CN108722437A - The preparation method and ferronickel composite catalyst of ferronickel composite catalyst - Google Patents
The preparation method and ferronickel composite catalyst of ferronickel composite catalyst Download PDFInfo
- Publication number
- CN108722437A CN108722437A CN201810574985.7A CN201810574985A CN108722437A CN 108722437 A CN108722437 A CN 108722437A CN 201810574985 A CN201810574985 A CN 201810574985A CN 108722437 A CN108722437 A CN 108722437A
- Authority
- CN
- China
- Prior art keywords
- composite catalyst
- nickel foam
- preparation
- ferronickel composite
- hydro
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- 229910000863 Ferronickel Inorganic materials 0.000 title claims abstract description 59
- 239000002131 composite material Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 118
- 239000006260 foam Substances 0.000 claims abstract description 59
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 230000007935 neutral effect Effects 0.000 claims abstract description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000872 buffer Substances 0.000 claims abstract description 28
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 25
- 238000005554 pickling Methods 0.000 claims abstract description 24
- 239000008367 deionised water Substances 0.000 claims abstract description 23
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 23
- 239000000243 solution Substances 0.000 claims abstract description 23
- 239000007864 aqueous solution Substances 0.000 claims abstract description 21
- 230000036647 reaction Effects 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000004140 cleaning Methods 0.000 claims abstract description 15
- SDLBJIZEEMKQKY-UHFFFAOYSA-M silver chlorate Chemical compound [Ag+].[O-]Cl(=O)=O SDLBJIZEEMKQKY-UHFFFAOYSA-M 0.000 claims abstract description 15
- 239000004575 stone Substances 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 29
- JKMHFZQWWAIEOD-UHFFFAOYSA-N 2-[4-(2-hydroxyethyl)piperazin-1-yl]ethanesulfonic acid Chemical compound OCC[NH+]1CCN(CCS([O-])(=O)=O)CC1 JKMHFZQWWAIEOD-UHFFFAOYSA-N 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims 3
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 claims 2
- WFCSWCVEJLETKA-UHFFFAOYSA-N 2-piperazin-1-ylethanol Chemical class OCCN1CCNCC1 WFCSWCVEJLETKA-UHFFFAOYSA-N 0.000 claims 1
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 239000007853 buffer solution Substances 0.000 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 238000009792 diffusion process Methods 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 3
- 239000000843 powder Substances 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 238000005868 electrolysis reaction Methods 0.000 description 6
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000001548 drop coating Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004577 artificial photosynthesis Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J25/00—Catalysts of the Raney type
- B01J25/02—Raney nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/06—Washing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Plasma & Fusion (AREA)
- Electrochemistry (AREA)
- Thermal Sciences (AREA)
- Optics & Photonics (AREA)
- Catalysts (AREA)
Abstract
The preparation method of ferronickel composite catalyst provided by the invention, is immersed in after the nickel foam after pickling is cleaned with deionized water in ethanol solution；The nickel foam after deionized water cleaning is taken out, and hydro-thermal reaction is carried out with alkaline aqueous solution；Using the nickel foam after hydro-thermal reaction as working electrode, silver-colored silver chlorate be reference electrode, stone mill stick is the cell reaction in neutral buffer to electrode；Nickel foam after cell reaction is cleaned by ultrasonic, obtain shaggy ferronickel composite catalyst, the preparation method of ferronickel composite catalyst provided by the invention, using porous foam nickel as conductive substrates, firm coarse ferronickel composite catalyst is synthesized by two-step process, it is with a large amount of active site, open ion diffusion admittance, excellent electric conductivity, firm combination, the problem of catalytic current has obtained significantly being promoted compared with existing powder catalyst, solves under the conditions of superhigh-current-density, existing poor catalyst stability.
Description
Technical field
It is multiple that the present invention relates to the preparation methods and ferronickel of a kind of composite catalyst more particularly to a kind of ferronickel composite catalyst
Close catalyst.
Background technology
Artificial photosynthesis based on water decomposition are a kind of effective ways storing solar energy in a manner of Hydrogen Energy.Artificial
In photosynthesis, it is the important reaction of a step that water, which resolves into oxygen,.Water oxidation reaction is due to higher energy consumption and slowly
Dynamics becomes the bottleneck of water decomposition reaction.Therefore designing the oxygen evolution reaction catalysts of efficient stable becomes the pass solved the problems, such as
Key.
Currently, the research of cheap transition metal based catalysts has been achieved for preliminary progress, but there are still very
More problems.For large-scale industrial production, on the one hand, commercialized noble metal catalyst is of high cost, develops low cost
And efficiently catalyst is imperative.On the other hand, the material in the case where high current generates of cheap transition catalyst at this stage
Material stability can't be protected.Also, catalytic process energy consumption is big and current density also needs to prodigious promotion, not up to
Commercial Application requirement.
Invention content
Have in view of that, it is necessary in view of the defects existing in the prior art, provide a kind of in holding super-active, very high current
The preparation method of ferronickel composite catalyst that is lower and having good stability.
To achieve the above object, the present invention uses following technical proposals:
On the one hand, the preparation method of ferronickel composite catalyst provided by the invention, includes the following steps：
Nickel foam is subjected to pickling processes；
It is immersed in ethanol solution after nickel foam after pickling is cleaned with deionized water；
The nickel foam after deionized water cleaning is taken out, and hydro-thermal reaction, the alkaline aqueous solution are carried out with alkaline aqueous solution
In be added with sodium hypochlorite；
Using the nickel foam after hydro-thermal reaction as working electrode, silver-colored silver chlorate be reference electrode, stone mill stick be to electrode, in
Cell reaction in neutral buffer, the neutral buffer is 4- hydroxyethyl piperazineethanesulfonic acid neutral buffers, described
4- hydroxyethyl piperazineethanesulfonic acids neutral buffer is also added with frerrous chloride；
Nickel foam after cell reaction is cleaned by ultrasonic, shaggy ferronickel composite catalyst is obtained.
In some preferred embodiment, in the step of nickel foam is carried out pickling processes, the pickling is molten using HCl/water
Liquid, a concentration of 0.5-3mol/L of the HCl/water solution.
In some preferred embodiment, the sodium hypochlorite mole is 0.001~0.1mol.
In some preferred embodiment, the nickel foam after taking out deionized water cleaning, and carry out water with alkaline aqueous solution
In the step of thermal response, the alkaline aqueous solution is the aqueous solution of potassium hydroxide.
In some preferred embodiment, the nickel foam after taking out deionized water cleaning, and carry out water with alkaline aqueous solution
In the step of thermal response, the temperature of the hydro-thermal reaction is 100-160 DEG C, and the time of the hydro-thermal reaction is 2-10h.
In some preferred embodiment, it is being reference using the nickel foam after hydro-thermal reaction as working electrode, silver-colored silver chlorate
Electrode, stone mill stick be to electrode, in neutral buffer the step of cell reaction in, the voltage of the cell reaction is 0.8-
1.8V constant voltages, cell reaction time are 100~1000s.
In some preferred embodiment, the voltage of the cell reaction is 1.2-1.4V constant voltages, and the cell reaction time is
200~500s.
In some preferred embodiment, the neutral buffer is also passed through argon gas to remove deoxidation before cell reaction
Gas.
In some preferred embodiment, a concentration of 0.1- of the 4- hydroxyethyl piperazineethanesulfonic acids neutral buffer
1mol/L, a concentration of 10-30 μm of ol of frerrous chloride.
In addition, the present invention also provides the ferronickel composite catalysts being prepared by above-mentioned preparation method.
The present invention uses above-mentioned technical proposal, can realize following advantageous effects：
The preparation method of ferronickel composite catalyst provided by the invention, after the nickel foam after pickling is cleaned with deionized water
It is immersed in ethanol solution；The nickel foam after deionized water cleaning is taken out, and hydro-thermal reaction is carried out with alkaline aqueous solution；By hydro-thermal
Nickel foam after reaction is as working electrode, silver-colored silver chlorate is reference electrode, stone mill stick is to electrode, in neutral buffer
Cell reaction；Nickel foam after cell reaction is cleaned by ultrasonic, shaggy ferronickel composite catalyst is obtained, the present invention provides
The preparation method of ferronickel composite catalyst pass through two steps using the porous foam nickel after pickling, hydro-thermal process as conductive substrates
The firm coarse ferronickel composite catalyst of method synthesis, the ferronickel composite catalyst being prepared by the above method have a large amount of
Active site, open ion diffusion admittance, excellent electric conductivity, firm combination, with existing powder catalyst
It has obtained significantly being promoted compared to catalytic current, solve under the conditions of superhigh-current-density, existing poor catalyst stability
Problem.
In addition, ferronickel composite catalyst prepared by the present invention, raw material sources are abundant, cheap, both had better
Catalytic activity, in turn ensure the stability of long-time service, commercialized noble metal catalyst at this stage can be substituted, be suitble to big
Technical scale produces.
Description of the drawings
Fig. 1 is the step flow chart of the preparation method of ferronickel composite catalyst provided by the invention.
Fig. 2 is the high power SEM spectrum of coarse ferronickel composite catalyst prepared by the embodiment of the present invention 1.
Fig. 3 is the high power SEM spectrum of coarse ferronickel composite catalyst prepared by the embodiment of the present invention 2.
Fig. 4 is the high power SEM spectrum of coarse ferronickel composite catalyst prepared by the embodiment of the present invention 3.
Fig. 5 is the high power SEM spectrum of coarse ferronickel composite catalyst prepared by the embodiment of the present invention 4.
Fig. 6 is that the Ir/C of coarse ferronickel composite catalyst and drop coating in nickel foam that the present invention is prepared with embodiment 1 is
Working electrode, silver-colored silver chlorate are reference electrode, and stone mill stick is to form three-electrode system to electrode, in 5mol/L potassium hydroxide solutions
The linear sweep voltammetry curve graph of middle electrolysis water oxygen evolution reaction.
Fig. 7 is that the Ir/C of the coarse ferronickel composite catalyst and drop coating of the preparation of the embodiment of the present invention 1 in nickel foam is work
Make electrode, silver-colored silver chlorate is reference electrode, and stone mill stick is to form three-electrode system to electrode, in 5mol/L potassium hydroxide solutions
Constant voltage 1.65V chronoptentiometry curve graphs.
Specific implementation mode
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.
Referring to Fig. 1, the preparation method of ferronickel composite catalyst provided by the invention, includes the following steps：
Step S110：Nickel foam is subjected to pickling processes.
Preferably, the pickling uses HCl/water solution, a concentration of 0.5-3mol/L of the HCl/water solution, pickling time
It is 30 minutes.
Step S120：It is immersed in ethanol solution after nickel foam after pickling is cleaned with deionized water.
Preferably, the nickel foam after pickling is cleaned to be immersed in afterwards three times in ethanol solution with deionized water and is stored for use.
Step S130：The nickel foam after deionized water cleaning is taken out, and hydro-thermal reaction, the alkali are carried out with alkaline aqueous solution
Property aqueous solution in be added with sodium hypochlorite.
Preferably, the sodium hypochlorite mole is 0.001~0.1mol, and the alkaline aqueous solution is the water of potassium hydroxide
Solution.
Further, the temperature of the hydro-thermal reaction is 100-160 DEG C, and the time of the hydro-thermal reaction is 2-10h.
Step S140：Using the nickel foam after hydro-thermal reaction as working electrode, silver-colored silver chlorate be reference electrode, stone mill stick is
To electrode, the cell reaction in neutral buffer, the neutral buffer is 4- hydroxyethyl piperazineethanesulfonic acid neutral buffereds
Solution, the 4- hydroxyethyl piperazineethanesulfonic acids neutral buffer are also added with frerrous chloride；
Preferably, the voltage of the cell reaction is 0.8-1.8V constant voltages, and the cell reaction time is 100~1000s, institute
State a concentration of 0.1-1mol/L of 4- hydroxyethyl piperazineethanesulfonic acid neutral buffers, a concentration of 10-30 μ of frerrous chloride
mol。
Further, the neutral buffer is also passed through argon gas to remove oxygen before cell reaction.
Step S150：Nickel foam after cell reaction is cleaned by ultrasonic, shaggy ferronickel composite catalyst is obtained.
The preparation method of ferronickel composite catalyst provided by the invention, with the porous foam nickel after pickling, hydro-thermal process
For conductive substrates, firm coarse ferronickel composite catalyst, the ferronickel being prepared by the above method is synthesized by two-step process
Composite catalyst, have a large amount of active site, open ion diffusion admittance, excellent electric conductivity, firm combination,
Catalytic current has obtained significantly being promoted compared with existing powder catalyst, solves under the conditions of superhigh-current-density, existing
There is the problem of poor catalyst stability.
In addition, ferronickel composite catalyst prepared by the present invention, raw material sources are abundant, cheap, both had better
Catalytic activity, in turn ensure the stability of long-time service, commercialized noble metal catalyst at this stage can be substituted, be suitble to big
Technical scale produces.
Above-mentioned technical proposal of the present invention is described in detail below in conjunction with specific embodiment.
Embodiment 1
Step S1：By nickel foam in 3mol/L HCl/water solution pickling processes 30 minutes；
Step S2：Deionized water cleaning after pickling is immersed in afterwards three times in ethanol solution and is stored for use；
Step S3：The nickel foam after deionized water cleaning is taken out, and nickel foam is placed in 100ml reaction kettles, addition contains
There is the aqueous solution of the alkaline potassium hydroxide of 0.002mol sodium hypochlorite, in an oven 100 DEG C of hydro-thermal reaction 10h；
Step S4：Using the foam nickel material of step S2 processing as working electrode, silver-colored silver chlorate be reference electrode, stone mill stick is
To electrode, 10 μm of ol protochlorides are rapidly added in the 4- hydroxyethyl piperazineethanesulfonic acid neutral buffers of 0.1mol/L pH=7
Iron adds 0.8V constant-potential electrolysis 1000s, wherein 4- hydroxyethyl piperazineethanesulfonic acids neutral buffer is also logical before reactions
30min argon gas is to remove oxygen.
Step S5：Treated, and nickel foam is cleaned with water and EtOH Sonicate, obtains coarse ferronickel composite catalyst.
Referring to Fig. 2, the high power SEM spectrum of the coarse ferronickel composite catalyst prepared for the embodiment of the present invention 2.
Embodiment 2
Step S1：By nickel foam in 0.5mol/L HCl/water solution pickling processes 30 minutes；
Step S2：Deionized water cleaning after pickling is immersed in afterwards three times in ethanol solution and is stored for use；
Step S3：The nickel foam after deionized water cleaning is taken out, and nickel foam is placed in 100ml reaction kettles, addition contains
There is the aqueous solution of the alkaline potassium hydroxide of 0.005mol sodium hypochlorite, in an oven 160 DEG C of hydro-thermal reaction 2h；
Step S4：Using the foam nickel material of step S2 processing as working electrode, silver-colored silver chlorate be reference electrode, stone mill stick is
To electrode, 10 μm of ol protochlorides are rapidly added in the 4- hydroxyethyl piperazineethanesulfonic acid neutral buffers of 0.1mol/L pH=7
Iron adds 1.8V constant-potential electrolysis 100s, wherein 4- hydroxyethyl piperazineethanesulfonic acids neutral buffer is also logical before reactions
30min argon gas is to remove oxygen.
Step S5：Treated, and nickel foam is cleaned with water and EtOH Sonicate, obtains coarse ferronickel composite catalyst.
Referring to Fig. 3, the high power SEM spectrum of the coarse ferronickel composite catalyst prepared for the embodiment of the present invention 2.
Embodiment 3
Step S1：By nickel foam in 2mol/L HCl/water solution pickling processes 30 minutes；
Step S2：Deionized water cleaning after pickling is immersed in afterwards three times in ethanol solution and is stored for use；
Step S3：The nickel foam after deionized water cleaning is taken out, and nickel foam is placed in 100ml reaction kettles, addition contains
There is the aqueous solution of the alkaline potassium hydroxide of 0.1mol sodium hypochlorite, in an oven 120 DEG C of hydro-thermal reaction 8h；
Step S4：The foam nickel material handled using step 2 is working electrode, silver-colored silver chlorate is reference electrode, stone mill stick is
To electrode, 10 μm of ol protochlorides are rapidly added in the 4- hydroxyethyl piperazineethanesulfonic acid neutral buffers of 0.1mol/L pH=7
Iron adds 1.1V constant-potential electrolysis 500s, wherein 4- hydroxyethyl piperazineethanesulfonic acids neutral buffer is also logical before reactions
30min argon gas is to remove oxygen.
Step S5：Treated, and nickel foam is cleaned with water and EtOH Sonicate, obtains coarse ferronickel composite catalyst,.
Referring to Fig. 4, the high power SEM spectrum of the coarse ferronickel composite catalyst prepared for the embodiment of the present invention 3.
Embodiment 4
Step S1：By nickel foam in 2mol/L HCl/water solution pickling processes 30 minutes；
Step S2：Deionized water cleaning after pickling is immersed in afterwards three times in ethanol solution and is stored for use；
Step S3：The nickel foam after deionized water cleaning is taken out, and nickel foam is placed in 100ml reaction kettles, addition contains
There is the aqueous solution of the alkaline potassium hydroxide of 0.002mol sodium hypochlorite, in an oven 120 DEG C of hydro-thermal reaction 8h；
Step S4：The foam nickel material handled using step 2 is working electrode, silver-colored silver chlorate is reference electrode, stone mill stick is
To electrode, 10 μm of ol protochlorides are rapidly added in the 4- hydroxyethyl piperazineethanesulfonic acid neutral buffers of 0.1mol/L pH=7
Iron adds 1.4V constant-potential electrolysis 300s, wherein 4- hydroxyethyl piperazineethanesulfonic acids neutral buffer is also logical before reactions
30min argon gas is to remove oxygen.
Step S5：Treated, and nickel foam is cleaned with water and EtOH Sonicate, obtains coarse ferronickel composite catalyst.
Referring to Fig. 5, the high power SEM spectrum of the coarse ferronickel composite catalyst prepared for the embodiment of the present invention 4.
In order to prove beneficial effects of the present invention, the coarse ferronickel composite catalyst and drop coating that are prepared using embodiment 1 are existed
Ir/C in nickel foam is as working electrode, silver-colored silver chlorate is reference electrode, stone mill stick is to build three-electrode system to electrode.
Two kinds of electrode systems are placed in 5mol/L KOH solutions and carry out electrolysis water oxygen evolution reaction activity test, electricity has been carried out in test process
Resistance compensation, is as a result shown in Fig. 6.
By Fig. 6 as it can be seen that compared with commercialized Ir/C, coarse ferronickel composite catalyst has higher catalytic activity,
In 2000mA/cm2And 4000mA/cm2When ferronickel composite catalyst need overpotential be only 313mV and 375mV.
Inventor is further using the coarse ferronickel composite catalyst and drop coating prepared using embodiment 1 in nickel foam
Ir/C is as working electrode, silver-colored silver chlorate is reference electrode, stone mill stick is to build three-electrode system to electrode.Above-mentioned structure
Two three-electrode systems carry out stability test in 5mol/L KOH aqueous solutions, and test uses chronoptentiometry, test process
In do not carry out resnstance transformer, as a result see Fig. 7.
As seen from Figure 7, coarse ferronickel composite catalyst activity higher, more steady compared with commercialized Ir/C catalyst
Fixed, in 80h electrolytic processes, electric current is stablized in 1000mA/cm always2Left and right, in the case where a large amount of bubbles generate, ferronickel is multiple
It closes catalyst and still shows long-time stability.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement etc., should all be included in the protection scope of the present invention made by within refreshing and principle.
Claims (10)
1. a kind of preparation method of ferronickel composite catalyst, which is characterized in that include the following steps：
Nickel foam is subjected to pickling processes；
It is immersed in ethanol solution after nickel foam after pickling is cleaned with deionized water；
The nickel foam after deionized water cleaning is taken out, and hydro-thermal reaction is carried out with alkaline aqueous solution, is added in the alkaline aqueous solution
Added with sodium hypochlorite；
Using the nickel foam after hydro-thermal reaction as working electrode, silver-colored silver chlorate be reference electrode, stone mill stick is to electrode, in neutrality
Cell reaction in buffer solution, the neutral buffer are 4- hydroxyethyl piperazineethanesulfonic acid neutral buffers, the 4- hydroxyls
Ethyl piperazidine ethanesulfonic acid neutral buffer is also added with frerrous chloride；
Nickel foam after cell reaction is cleaned by ultrasonic, shaggy ferronickel composite catalyst is obtained.
2. the preparation method of ferronickel composite catalyst according to claim 1, which is characterized in that nickel foam is being carried out acid
In the step of washing processing, the pickling uses HCl/water solution, a concentration of 0.5-3mol/L of the HCl/water solution.
3. the preparation method of ferronickel composite catalyst according to claim 1, which is characterized in that the sodium hypochlorite mole
Amount is 0.001~0.1mol.
4. the preparation method of ferronickel composite catalyst according to claim 3, which is characterized in that taking out, deionized water is clear
Nickel foam after washing, and in the step of carrying out hydro-thermal reaction with alkaline aqueous solution, the alkaline aqueous solution is the water of potassium hydroxide
Solution.
5. the preparation method of ferronickel composite catalyst according to claim 3, which is characterized in that taking out, deionized water is clear
Nickel foam after washing, and in the step of carrying out hydro-thermal reaction with alkaline aqueous solution, the temperature of the hydro-thermal reaction is 100-160
DEG C, the time of the hydro-thermal reaction is 2-10h.
6. the preparation method of ferronickel composite catalyst according to claim 1, which is characterized in that after by hydro-thermal reaction
Nickel foam is as working electrode, silver-colored silver chlorate is reference electrode, stone mill stick is the cell reaction in neutral buffer to electrode
The step of in, the voltage of the cell reaction is 0.8-1.8V constant voltages, and the cell reaction time is 100~1000s.
7. the preparation method of ferronickel composite catalyst according to claim 6, which is characterized in that the electricity of the cell reaction
Pressure is 1.2-1.4V constant voltages, and the cell reaction time is 200~500s.
8. the preparation method of ferronickel composite catalyst according to claim 6, which is characterized in that the neutral buffer
Argon gas is also passed through before cell reaction to remove oxygen.
9. the preparation method of ferronickel composite catalyst according to claim 6, which is characterized in that the 4- hydroxyethyl piperazines
A concentration of 0.1-1mol/L of ethanesulfonic acid neutral buffer, a concentration of 10-30 μm of ol of frerrous chloride.
10. a kind of ferronickel composite catalyst, which is characterized in that by the preparation side for the ferronickel composite catalyst that claim 1 provides
Method is prepared.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810574985.7A CN108722437A (en) | 2018-06-06 | 2018-06-06 | The preparation method and ferronickel composite catalyst of ferronickel composite catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810574985.7A CN108722437A (en) | 2018-06-06 | 2018-06-06 | The preparation method and ferronickel composite catalyst of ferronickel composite catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108722437A true CN108722437A (en) | 2018-11-02 |
Family
ID=63932440
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810574985.7A Pending CN108722437A (en) | 2018-06-06 | 2018-06-06 | The preparation method and ferronickel composite catalyst of ferronickel composite catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108722437A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110863211A (en) * | 2019-11-14 | 2020-03-06 | 南通大学 | Electrode for hydrothermal oxidation treatment under alkaline condition and preparation method thereof |
| CN110820012B (en) * | 2019-11-14 | 2021-07-09 | 南通大学 | Electrode modification method based on acid thermal reflux treatment |
| WO2024002126A1 (en) * | 2022-07-01 | 2024-01-04 | 中国科学院大连化学物理研究所 | Preparation method for one-dimensional ni12p5/ni2p polycrystalline heterostructure catalyst used for efficient water oxidation |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016023065A1 (en) * | 2014-08-11 | 2016-02-18 | Newsouth Innovations Pty Limited | Catalytic assembly |
| CN107045947A (en) * | 2017-04-14 | 2017-08-15 | 武汉理工大学 | A kind of iron nickel binary oxide nickel foam combination electrode material and preparation method thereof |
| CN107620087A (en) * | 2016-07-15 | 2018-01-23 | 中国科学院大连化学物理研究所 | A kind of FeOOH nickel-ferric spinel integration analysis oxygen electrode and preparation and application |
| CN108097270A (en) * | 2017-12-20 | 2018-06-01 | 青岛大学 | A kind of elctro-catalyst for being catalyzed water decomposition production hydrogen and its preparation method and application |
-
2018
- 2018-06-06 CN CN201810574985.7A patent/CN108722437A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016023065A1 (en) * | 2014-08-11 | 2016-02-18 | Newsouth Innovations Pty Limited | Catalytic assembly |
| CN107620087A (en) * | 2016-07-15 | 2018-01-23 | 中国科学院大连化学物理研究所 | A kind of FeOOH nickel-ferric spinel integration analysis oxygen electrode and preparation and application |
| CN107045947A (en) * | 2017-04-14 | 2017-08-15 | 武汉理工大学 | A kind of iron nickel binary oxide nickel foam combination electrode material and preparation method thereof |
| CN108097270A (en) * | 2017-12-20 | 2018-06-01 | 青岛大学 | A kind of elctro-catalyst for being catalyzed water decomposition production hydrogen and its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| MINGXING CHEN等: "An Iron-based Film for Highly Efficient Electrocatalytic Oxygen Evolution from Neutral Aqueous Solution", 《ACS APPL. MATER. INTERFACES》 * |
| WEI ZHANG等: "A Nickel-Based Integrated Electrode from an Autologous Growth Strategy for Highly Efficient Water Oxidation", 《ADV. ENERGY MATER.》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110863211A (en) * | 2019-11-14 | 2020-03-06 | 南通大学 | Electrode for hydrothermal oxidation treatment under alkaline condition and preparation method thereof |
| CN110863211B (en) * | 2019-11-14 | 2021-04-27 | 南通大学 | Electrode for hydrothermal oxidation treatment under alkaline condition and preparation method thereof |
| CN110820012B (en) * | 2019-11-14 | 2021-07-09 | 南通大学 | Electrode modification method based on acid thermal reflux treatment |
| WO2024002126A1 (en) * | 2022-07-01 | 2024-01-04 | 中国科学院大连化学物理研究所 | Preparation method for one-dimensional ni12p5/ni2p polycrystalline heterostructure catalyst used for efficient water oxidation |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110331414B (en) | MOF (Metal organic framework) composite copper-based nanorod array @ foam copper-based composite electrode material as well as preparation method and application thereof | |
| CN104846397B (en) | One kind being used for electrochemical reduction CO2The electrode and its preparation method and application of formic acid processed | |
| CN105483747B (en) | A kind of method and device of water electrolysis hydrogen production gas | |
| CN103422116B (en) | A kind of porous Ni-base ru oxide is combined the preparation method of hydrogen-precipitating electrode | |
| CN103820807A (en) | Device and method for producing hydrogen and generating electricity | |
| CN111686736B (en) | Preparation method of NiFe-LDH/NF three-dimensional self-supporting electrolytic water oxygen evolution catalyst containing high-activity high-valence iron | |
| CN107868959B (en) | Etching method for increasing electrochemical active area of foamed nickel electrode | |
| CN113151843A (en) | Method and device for producing hydrogen by electrolyzing water step by step | |
| CN105951117B (en) | A kind of electrolytic method of low cost production high purity of hydrogen peroxide and hydrogen | |
| CN108425144B (en) | Preparation method of karst foam nickel for producing oxygen by electrocatalytic total decomposition of hydrogen in water | |
| CN103668342B (en) | A kind of manganese electrolysis titanium based composite anode and preparation method | |
| CN108722437A (en) | The preparation method and ferronickel composite catalyst of ferronickel composite catalyst | |
| CN110952111A (en) | Two-step oxidation synthesized electrolytic water anode and preparation method thereof | |
| CN107999075A (en) | A kind of aza material preparation method of NiO nanoparticle doped carbon and application | |
| CN103924263A (en) | Preparation method of high-performance nickel-based ruthenium-containing compound oxide hydrogen evolution electrode | |
| CN111672520B (en) | Amorphous cobalt borate-nickel selenide @ foam nickel compound, preparation method and application | |
| CN113249740A (en) | Method for preparing graphene by electrochemical continuous and synchronous stripping and reduction | |
| CN106521550B (en) | Nickel foam/LBL self-assembly carbon nanotube/nickel composite material preparation method for electrolytic hydrogen production | |
| CN213570766U (en) | Water decomposition hydrogen production device based on lead net | |
| CN113249743B (en) | Catalyst for electrocatalytic oxidation of glycerol and preparation method thereof | |
| CN109402654A (en) | A kind of MoS with substrate protective function2/Ni3Se2Compound Electrocatalytic Activity for Hydrogen Evolution Reaction agent and preparation method thereof | |
| CN216738553U (en) | Step-by-step water electrolysis hydrogen production device | |
| CN110965075A (en) | Preparation and application of carbon dioxide electrochemical reduction electrode | |
| CN110137523A (en) | A kind of new hydrogen production hydrazine hydrate fuel-cell device | |
| CN101864578A (en) | Method for preparing peroxysulfuric acid by sonoelectrochemical method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181102 |
|
| RJ01 | Rejection of invention patent application after publication |