CN109453785A - A kind of meso-porous nano platinum nickel oxygen reduction electro-catalyst and preparation method thereof - Google Patents
A kind of meso-porous nano platinum nickel oxygen reduction electro-catalyst and preparation method thereof Download PDFInfo
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- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- SJFYULBPXZDOIR-UHFFFAOYSA-N nickel;oxoplatinum Chemical compound [Ni].[Pt]=O SJFYULBPXZDOIR-UHFFFAOYSA-N 0.000 title claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 90
- PCLURTMBFDTLSK-UHFFFAOYSA-N nickel platinum Chemical compound [Ni].[Pt] PCLURTMBFDTLSK-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000002105 nanoparticle Substances 0.000 claims abstract description 57
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 48
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 45
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 28
- 239000001301 oxygen Substances 0.000 claims abstract description 28
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims abstract description 25
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims abstract description 25
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 24
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 24
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 24
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 16
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000005119 centrifugation Methods 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- GDSOZVZXVXTJMI-SNAWJCMRSA-N (e)-1-methylbut-1-ene-1,2,4-tricarboxylic acid Chemical compound OC(=O)C(/C)=C(C(O)=O)\CCC(O)=O GDSOZVZXVXTJMI-SNAWJCMRSA-N 0.000 claims 2
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 230000001603 reducing effect Effects 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 description 33
- 239000003054 catalyst Substances 0.000 description 16
- 238000004502 linear sweep voltammetry Methods 0.000 description 14
- 230000003197 catalytic effect Effects 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 230000005611 electricity Effects 0.000 description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- 238000006479 redox reaction Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 206010013786 Dry skin Diseases 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000011549 displacement method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000009790 rate-determining step (RDS) Methods 0.000 description 2
- 238000001507 sample dispersion Methods 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
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- 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
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
A kind of mesoporous platinum nickel nano particle oxygen reduction electro-catalyst and preparation method match chloroplatinic acid and nickel chloride solution of the concentration between 4~40mM, ascorbic acid solution of the concentration between 0.05~0.5M respectively；The F127 of 5~50mg and 0.1~0.5g potassium bromide are dissolved in 0.1~3mL water；The platinum acid chloride solution of 0.5~2mL, the nickel chloride solution of 0~1mL, the ascorbic acid solution of 0.1~5mL and above-mentioned solution are mixed, it is placed in 50~100 DEG C of water-bath and reacts 5~30 hours, reaction terminates, centrifugation, washing obtain mesoporous platinum nickel nano particle, product is 10~14 hours dry at 40~60 DEG C, obtain mesoporous platinum nickel nano particle oxygen reduction electro-catalyst.Preparation process of the present invention is flexible, and under low-temperature atmosphere-pressure, material obtained has excellent electrocatalytic oxidation reducing property.
Description
(1) technical field
The present invention relates to a kind of meso-porous nano platinum nickel oxygen reduction electro-catalysts and preparation method thereof, which can be used for electricity
The research of catalytic oxidation-reduction reaction.
(2) background technique
Platinum is shown greatly due to its unique electronic structure in catalytic field as a member important in noble metal
Potentiality.Platinum based catalyst presents outstanding catalytic performance in fields such as chemical reaction, sensing and fuel cells.However it is some
Inevitable bottleneck prevents the large-scale use of platinum based catalyst, and the reserves including platinum are low, platinum based catalyst at high cost
And the catalytic stability of platinum based catalyst is poor in certain catalysis reactions.Therefore, develop high catalytic activity and low platinum catalysis
Agent is particularly significant.Due to these limitations, researcher is broadly directed to the size, shape, structure and composition of platinum based catalyst
Research.Platinum is metal element alloyed with other, especially base metal, is a up-and-coming strategy to maximally utilize
Platinum.It is reported that researcher synthesized the platinum base alloy nano wire of sub-micron enhance catalyst oxygen reduction performance (K.Jiang,
D.Zhao,S.Guo,X.Zhang,X.Zhu,J.Guo,G.Lu and X.Huang,Sci.Adv.,2017,3,E1601705)。
On the one hand, the dosage of platinum can directly be reduced by part platinum being substituted for second of metallic element, to reach the content of platinum in catalyst
Purpose.On the other hand, the introducing of alloying element can influence the electronic structure of platinum by straining with ligand effect.With regard to this
For point, there are many major progresses at present for control synthesis platinum bimetallic nanostructure.Wherein, bimetallic platinum nickel nanocrystal quilt
It is considered the elctro-catalyst of a classical hydrogen reduction, and is widely used in the cathode reaction of fuel cell.
Structure design is another effective ways for adjusting platinum base nano material catalytic performance.In nano-scale, reasonably
The structure for regulating and controlling platinum-base material, is conducive to expose pt atom in catalyst surface, while can also provide higher catalytic activity.
Porous nanometer structure has shown a series of advantage, including large specific surface area, active site abundant in catalytic field
With efficient quickly transfer reaction object etc..Before this, researcher is by removing alloyage, electric displacement method, electrochemical deposition method and mould
A variety of strategies such as plate method have synthesized platinum porous structure, but it is most of can only synthesize irregular shape or reticular structure, essence
Really the morphology and size of control composition rule is still than relatively difficult to achieve.Therefore, simpler and efficient step is synthesis platinum nickel
The key of mesoporous catalyst.
(3) summary of the invention
The present invention relates to a kind of preparation method of meso-porous nano platinum nickel oxygen reduction electro-catalyst, which can be used for electricity and urges
Change the research of oxygen reduction reaction.
The technical solution adopted by the present invention is that:
A kind of mesoporous platinum nickel nano particle oxygen reduction electro-catalyst, prepares by the following method:
(1) match chloroplatinic acid and nickel chloride solution of the concentration between 4~40mM respectively, concentration is between 0.05~0.5M
Ascorbic acid solution；
(2) potassium bromide of the F127 of 5~50mg and 0.1~0.5g is dissolved in 0.1~3mL water；
(3) by the platinum acid chloride solution of 0.5~2mL, the nickel chloride solution of 0~1mL, 0.1~5mL ascorbic acid solution and
The solution of step (2) mixes, and is placed in 50~100 DEG C of water-bath and reacts 5~30 hours, and reaction terminates, and centrifugation, washing are situated between
Hole platinum nickel nano particle, product is 10~14 hours dry at 40~60 DEG C, it obtains mesoporous platinum nickel nano particle hydrogen reduction electricity and urges
Agent.
The selection of reaction condition has great influence to the structure for preparing mesoporous platinum nickel nano particle.Surfactant F127
It plays an important role in preparing mesoporous platinum nickel nano particle, as Micellar Gel, F127 can effectively instruct mesoporous platinum
The synthesis of nickel nano particle.
A kind of preparation method of meso-porous nano platinum nickel oxygen reduction electro-catalyst, described method includes following steps:
(1) match chloroplatinic acid and nickel chloride solution of the concentration between 4~40mM respectively, concentration is between 0.05~0.5M
Ascorbic acid solution；
(2) F127 of 5~50mg and 0.1~0.5g potassium bromide are dissolved in 0.1~3mL water；
(3) by the platinum acid chloride solution of 0.5~2mL, the nickel chloride solution of 0~1mL, 0.1~5mL ascorbic acid solution and
The solution of step (2) mixes, and is placed in 50~100 DEG C of water-bath and reacts 5~30 hours, and reaction terminates, and centrifugation, washing are situated between
Hole platinum nickel nano particle, product is 10~14 hours dry at 40~60 DEG C, it obtains mesoporous platinum nickel nano particle hydrogen reduction electricity and urges
Agent.
Further, the concentration and volume of chloroplatinic acid and ascorbic acid, the type of surfactant, and the temperature of reaction are controlled
Degree and time control the pattern and structure of mesoporous platinum Raney nickel.
Electrochemical catalytic oxidation reduction reaction, performance test operating process are carried out at normal temperatures and pressures are as follows:
(1) sample dispersion of 1~10mg is weighed in ultrapure water, and ultrasound obtains uniform dispersion liquid in 30 minutes, takes 1~10
The Nafion solution (0.5wt%) that the mixing drop of μ L drips 1~10 μ L again after glassy carbon electrode surface, 50 DEG C of dryings, which is covered on, urges
Agent surface, is made working electrode；Platinum electrode is used as to electrode simultaneously, and Ag/AgCl electrode is as three electricity of reference electrode composition
Electrode systems carry out hydrogen reduction test；
(2) before testing, the perchloric acid solution of 0.1M is added in electrolytic cell, logical 30 minutes oxygen keeps its solution oxygen full
With the test program of selection cyclic voltammetry and linear sweep voltammetry, with computer monitor working electrode in the case where difference sweeps speed
Current conditions；It is last to calculate Tafel slope according to the data measured and corresponding formula, shift electron number and peroxidating
Hydrogen yield evaluates the hydrogen reduction performance of catalyst.
The present invention devises a kind of synthetic method of universality to prepare mesoporous platinum nickel nano particle.Have benefited from component and knot
The synergistic effect of structure, this design can effectively enhance the catalytic activity and stability of redox reaction.Compared to removing alloy
Method, electrochemical displacement method and seed mediated growth method, the design is simply direct, this promotes electrochemical applications tool to research platinum-base material
There is important meaning.
The main body of beneficial effect of the controllable method for preparing of mesoporous platinum nickel nano particle elctro-catalyst provided by the present invention
It is present:
(1) product can be directly obtained under low temperature, reasonably using surfactant F127 as soft template and pore creating material, closed
At mesoporous platinum nickel nano particle uniform particle sizes, pattern is uniform, and yield is almost 100%.
(2) the mesoporous platinum nickel nano particle elctro-catalyst synthesized presents activity outstanding and is stablized in oxygen reduction reaction
Property, platinum-base material has very high application prospect as elctro-catalyst.
(4) Detailed description of the invention
Fig. 1 is that the SEM of the mesoporous platinum nickel nano particle of specific embodiments of the present invention 1 schemes.
Fig. 2 is that the TEM and HRTEM of the mesoporous platinum nickel nano particle of specific embodiments of the present invention 1 scheme
Fig. 3 is the XRD diagram of the mesoporous platinum nickel nano particle of specific embodiments of the present invention 1.
Fig. 4 is that the XPS of the mesoporous platinum nickel nano particle of specific embodiments of the present invention 1 schemes.
Fig. 5 is linear sweep voltammetry curve of the mesoporous platinum nickel nano particle of specific embodiments of the present invention 1 under 1600 turns,
Tafel slope figure.
Fig. 6 is the linear sweep voltammetry curve under the mesoporous platinum nickel nano particle every speed of specific embodiments of the present invention 1
And transfer electron number.Rotation ring disk electrode electric current shifts electron number and hydrogen peroxide yield figure.
Fig. 7 is that linear sweep voltammetry of the mesoporous platinum nickel nano particle of specific embodiments of the present invention 1 before and after 1000 circles is bent
Line and polarogram current-time curvel figure.
Fig. 8 is that the SEM of the mesoporous nano platinum particle of specific embodiments of the present invention 2 schemes.
Fig. 9 is linear sweep voltammetry curve of the mesoporous nano platinum particle of specific embodiments of the present invention 2 under 1600 turns, tower
Fei Er slope figure.
(5) specific embodiment
The present invention is described further combined with specific embodiments below, but protection scope of the present invention is not limited in
This:
Referring to Fig.1~Fig. 7, in the present embodiment, the performance test to the hydrogen reduction of the platinum nickel material is in CHI 852D
It is carried out on electrochemical workstation, operating process are as follows:
The first step weighs the sample dispersion of 2mg in 1mL ultrapure water, and ultrasound obtains uniform dispersion liquid in 30 minutes, takes 5 μ
The Nafion solution (0.5wt%) that the mixing drop of L drips 5 μ L after glassy carbon electrode surface, 50 DEG C of dryings is covered on catalyst table
Working electrode is made in face.Platinum electrode is used as to electrode simultaneously, and Ag/AgCl electrode forms three-electrode system as reference electrode
Carry out redox test；
The perchloric acid solution of 0.1M is added before testing in second step in electrolytic cell, logical 30 minutes oxygen makes its solution oxygen
Saturation selects the test program of cyclic voltammetry and linear sweep voltammetry, sweeps speed in difference with computer monitor working electrode
Under current conditions.It is last to calculate Tafel slope according to the data measured and corresponding formula, shift electron number and peroxide
Change hydrogen yield to evaluate the hydrogen reduction performance of catalyst.
Embodiment 1
A kind of preparation method of mesoporous platinum nickel nano particle oxygen reduction electro-catalyst, described method includes following steps:
(1) chloroplatinic acid and nickel chloride solution for being respectively 20mM with concentration, concentration are the ascorbic acid solution of 0.1M；
(2) F127 the and 0.2g potassium bromide of 30mg is dissolved in 1.25mL water；
(3) by the platinum acid chloride solution of 1.125mL, the nickel chloride solution of 0.375mL, the ascorbic acid solution of 2mL and step
(2) solution mixing, is placed in 70 DEG C of water-bath and reacts 12 hours, and reaction terminates, and centrifugation, washing obtain mesoporous platinum nickel nanoparticle
Son, product is 12 hours dry at 50 DEG C, obtain mesoporous platinum nickel nano particle oxygen reduction electro-catalyst.
The SEM figure of the mesoporous platinum nickel nano particle obtained is referring to Fig. 1.Obtain mesoporous platinum nickel nano particle TEM and
HRTEM schemes referring to fig. 2.The XRD diagram of the mesoporous platinum nickel nano particle obtained is referring to Fig. 3.The mesoporous platinum nickel nano particle obtained
XPS schemes referring to fig. 4.Linear sweep voltammetry of the mesoporous platinum nickel nano particle obtained under 1600 turns, Tafel slope is referring to figure
5.Linear sweep voltammetry and transfer electron number under every speed is referring to Fig. 6.The rotating ring of the mesoporous platinum nickel nano particle obtained
Disk electric current shifts electron number and hydrogen peroxide yield referring to Fig. 6.The linear sweep voltammetry curve and polarogram electricity of 1000 circle front and backs
Time graph is flowed referring to Fig. 7.
By SEM figure as it can be seen that mesoporous platinum nickel nano particle is uniform spherical structure, and can be clear that on surface
Continuous meso-hole structure, the yield of mesoporous platinum nickel nano particle is close to 100%.Surface point can be clear that by TEM figure
The presence of branch.Pass through HRTEM and XRD analysis, it was demonstrated that the face-centred cubic structure of metal is formed.By XPS analysis, there are zeroth order platinum
Metallic state is all reduced to the presoma of divalent platinum, platinum.It can be seen that the mesoporous platinum of shape of ringing a bell by linear sweep voltammetry curve
Take-off potential (1.02V vs.RHE) and half wave potential (0.89V vs.RHE) with the reaction of biggish catalytic oxidation-reduction.According to
Linear sweep voltammetry curve calculate Tafel slope be 66.8mV dec-1, it was demonstrated that the first electronics turns during hydrogen reduction
Shifting is rate determining step.By the linear sweep voltammetry curve under different rotating speeds and electron number is shifted, Rotation ring disk electrode electric current turns
Moving electron number and hydrogen peroxide yield can be seen that and four electron reactions have occurred, and intermediate product is few.Line from 1000 circle front and backs
Property scanning volt-ampere curve and polarogram current-time curvel can be seen that mesoporous platinum nickel nano particle with good stability.
Embodiment 2
A kind of mesoporous nano platinum particle oxygen reduction electro-catalyst preparation method, described method includes following steps:
(1) platinum acid chloride solution for being respectively 20mM with concentration, concentration are the ascorbic acid solution of 0.1M；
(2) F127 the and 0.2g potassium bromide of 30mg is dissolved in 1.25mL water；
(3) solution of the platinum acid chloride solution of 1.5mL, the ascorbic acid solution of 2mL and step (2) is mixed, is placed in 70 DEG C
Water-bath in react 12 hours, reaction terminates, and centrifugation, washing obtain mesoporous platinum nickel nano particle, by product at 50 DEG C dry 12
Hour, obtain mesoporous platinum nickel nano particle oxygen reduction electro-catalyst.
The SEM figure of the mesoporous nano platinum particle obtained is linear under 1600 turns of mesoporous nano platinum particle of acquisition referring to Fig. 8
Volt-ampere and Tafel slope are scanned referring to Fig. 9.
Schemed by SEM as it can be seen that mesoporous nano platinum particle is formed.It can be seen that mesoporous platinum by linear sweep voltammetry curve to receive
The take-off potential (0.98V vs.RHE) and half wave potential (0.88V vs.RHE) of rice cage catalytic oxidation-reduction reaction with higher.
According to linear sweep voltammetry curve calculate Tafel slope be 67.2mV dec-1, it was demonstrated that the first electronics during hydrogen reduction
Transfer be rate determining step.
Embodiment 3
A kind of preparation method of mesoporous platinum nickel nano particle oxygen reduction electro-catalyst, described method includes following steps:
(1) chloroplatinic acid and nickel chloride solution for being respectively 40mM with concentration, concentration are the ascorbic acid solution of 0.1M；
(2) F127 the and 0.2g potassium bromide of 30mg is dissolved in 1.25mL water；
(3) by the platinum acid chloride solution of 1.125mL, the nickel chloride solution of 0.375mL, the ascorbic acid solution of 2mL and step
(2) solution mixing, is placed in 70 DEG C of water-bath and reacts 12 hours, and reaction terminates, and centrifugation, washing obtain mesoporous platinum nickel nanoparticle
Son, product is 10 hours dry at 40 DEG C, obtain mesoporous platinum nickel nano particle oxygen reduction electro-catalyst.
Since in this synthesis process, chloroplatinic acid and nickel chloride solution concentration are too high, and reaction rate is too fast, cannot obtain
The uniform meso-hole structure of structure, therefore mesoporous platinum nickel nano particle oxygen reduction electro-catalyst expected from more difficult synthesis.
Embodiment 4
A kind of preparation method of mesoporous platinum nickel nano particle oxygen reduction electro-catalyst, described method includes following steps:
(1) chloroplatinic acid and nickel chloride solution for being respectively 4mM with concentration, concentration are the ascorbic acid solution of 0.1M；
(2) F127 the and 0.2g potassium bromide of 30mg is dissolved in 1.25mL water；
(3) by the platinum acid chloride solution of 1.125mL, the nickel chloride solution of 0.375mL, the ascorbic acid solution of 2mL and step
(2) solution mixing, is placed in 70 DEG C of water-bath and reacts 12 hours, and reaction terminates, and centrifugation, washing obtain mesoporous platinum nickel nanoparticle
Son, product is 14 hours dry at 60 DEG C, obtain mesoporous platinum nickel nano particle oxygen reduction electro-catalyst.
Since in this synthesis process, chloroplatinic acid and nickel chloride solution concentration are too low, and reaction rate is excessively slow, cannot obtain
The uniform meso-hole structure of structure, therefore mesoporous platinum nickel nano particle oxygen reduction electro-catalyst expected from more difficult synthesis.
Embodiment 5
A kind of preparation method of mesoporous platinum nickel nano particle oxygen reduction electro-catalyst, described method includes following steps:
(1) chloroplatinic acid and nickel chloride solution for being respectively 4mM with concentration, concentration are the ascorbic acid solution of 0.05M；
(2) F127 the and 0.1g potassium bromide of 5mg is dissolved in 0.1mL water；
(3) by the platinum acid chloride solution of 0.5mL, the nickel chloride solution of 0.1mL, the ascorbic acid solution of 0.1mL and step (2)
Solution mixing, be placed in 50 DEG C of water-bath and react 5 hours, reaction terminates, centrifugation, wash obtain mesoporous platinum nickel nano particle,
Product is 10 hours dry at 40 DEG C, obtain mesoporous platinum nickel nano particle oxygen reduction electro-catalyst.
Since in this synthesis process, chloroplatinic acid and nickel chloride solution concentration are too low, and ascorbic acid concentrations are too low, reaction
Rate is excessively slow, therefore mesoporous platinum nickel nano particle oxygen reduction electro-catalyst expected from more difficult synthesis.
Embodiment 6
A kind of preparation method of mesoporous platinum nickel nano particle oxygen reduction electro-catalyst, described method includes following steps:
(1) chloroplatinic acid and nickel chloride solution for being respectively 40mM with concentration, concentration are the ascorbic acid solution of 0.5M；
(2) F127 the and 0.5g potassium bromide of 50mg is dissolved in 3mL water；
(3) by the platinum acid chloride solution of 2mL, the nickel chloride solution of 1mL, the ascorbic acid solution of 5mL and step (2) solution
Mixing, is placed in 100 DEG C of water-bath and reacts 30 hours, and reaction terminates, and centrifugation, washing obtain mesoporous platinum nickel nano particle, will produce
Object is 14 hours dry at 60 DEG C, obtains mesoporous platinum nickel nano particle oxygen reduction electro-catalyst.
Since in this synthesis process, chloroplatinic acid and nickel chloride solution concentration are too high, and ascorbic acid concentrations are too high, reaction
Rate is too fast, and product is reunited seriously, therefore mesoporous platinum nickel nano particle oxygen reduction electro-catalyst expected from more difficult synthesis.
Claims (3)
1. a kind of meso-porous nano platinum nickel oxygen reduction electro-catalyst, which is characterized in that prepare by the following method:
(1) match chloroplatinic acid and nickel chloride solution of the concentration between 4~40mM respectively, concentration is anti-bad between 0.05~0.5M
Hematic acid solution；
(2) potassium bromide of the F127 of 5~50mg and 0.1~0.5g is dissolved in 0.1~3mL water；
(3) ascorbic acid solution of the platinum acid chloride solution of 0.5~2mL, the nickel chloride solution of 0~1mL, 0.1~5mL are added to
It in the solution of step (2), is placed in 50~100 DEG C of water-bath and reacts 5~30 hours, reaction terminates, and centrifugation, washing obtain mesoporous
Platinum nickel nano particle, product is 10~14 hours dry at 40~60 DEG C, obtain mesoporous platinum nickel nano particle hydrogen reduction electro-catalysis
Agent.
2. a kind of preparation method of mesoporous platinum nickel nano particle oxygen reduction electro-catalyst as described in claim 1, feature exist
In described method includes following steps:
(1) match chloroplatinic acid and nickel chloride solution of the concentration between 4~40mM respectively, concentration is anti-bad between 0.05~0.5M
Hematic acid solution；
(2) potassium bromide of the F127 of 5~50mg and 0.1~0.5g is dissolved in 0.1~3mL water；
(3) by the platinum acid chloride solution of 0.5~2mL, the nickel chloride solution of 0~1mL, the ascorbic acid solution of 0.1~5mL and step
(2) solution mixing, is placed in 50~100 DEG C of water-bath and reacts 5~30 hours, and reaction terminates, and centrifugation, washing obtain mesoporous platinum
Nickel nano particle, product is 10~14 hours dry at 40~60 DEG C, obtain mesoporous platinum nickel nano particle oxygen reduction electro-catalyst.
3. method according to claim 2, which is characterized in that the concentration and body of control chloroplatinic acid, nickel chloride and ascorbic acid
Product, the dosage of potassium bromide, the type of surfactant, and the temperature and time of reaction control the pattern and knot of platinum nickel material
Structure.
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