CN109364964A - A kind of platinum palladium nickel-phosphorus alloy porous nano microballoon and preparation method thereof of catalytic oxidation-reduction reaction - Google Patents
A kind of platinum palladium nickel-phosphorus alloy porous nano microballoon and preparation method thereof of catalytic oxidation-reduction reaction Download PDFInfo
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 162
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 153
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 80
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 76
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910001096 P alloy Inorganic materials 0.000 title claims abstract description 34
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 24
- 238000006479 redox reaction Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000243 solution Substances 0.000 claims abstract description 91
- 239000002253 acid Substances 0.000 claims abstract description 47
- 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 44
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 22
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 22
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 22
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 22
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 22
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 21
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000000460 chlorine Substances 0.000 claims abstract description 21
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 21
- 239000011734 sodium Substances 0.000 claims abstract description 21
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims abstract description 20
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims abstract description 20
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 18
- 230000001376 precipitating effect Effects 0.000 claims abstract description 18
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 16
- 229910000990 Ni alloy Inorganic materials 0.000 claims abstract description 14
- PCLURTMBFDTLSK-UHFFFAOYSA-N nickel platinum Chemical compound [Ni].[Pt] PCLURTMBFDTLSK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- 239000007864 aqueous solution Substances 0.000 claims abstract description 9
- 238000005119 centrifugation Methods 0.000 claims abstract description 9
- 239000002077 nanosphere Substances 0.000 claims abstract description 9
- 239000002244 precipitate Substances 0.000 claims abstract description 9
- 239000012901 Milli-Q water Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 8
- 239000008236 heating water Substances 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Inorganic materials [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 5
- 239000004094 surface-active agent Substances 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
- 239000003054 catalyst Substances 0.000 abstract description 20
- 239000000463 material Substances 0.000 abstract description 15
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 3
- 239000000047 product Substances 0.000 abstract description 3
- 230000001603 reducing effect Effects 0.000 abstract description 3
- 239000011259 mixed solution Substances 0.000 abstract 1
- 230000035484 reaction time Effects 0.000 abstract 1
- 238000002604 ultrasonography Methods 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 22
- 238000006722 reduction reaction Methods 0.000 description 16
- 230000009467 reduction Effects 0.000 description 12
- 238000004502 linear sweep voltammetry Methods 0.000 description 11
- 229910052759 nickel Inorganic materials 0.000 description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052698 phosphorus Inorganic materials 0.000 description 10
- 239000011574 phosphorus Substances 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 239000000956 alloy Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 238000012546 transfer Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 239000012488 sample solution Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229920000557 Nafion® Polymers 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- 238000011017 operating method Methods 0.000 description 2
- 238000009790 rate-determining step (RDS) Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- SGDPVQRGBHPKIH-UHFFFAOYSA-L [Ni].Cl[Ni]Cl Chemical compound [Ni].Cl[Ni]Cl SGDPVQRGBHPKIH-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000011807 nanoball Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 229910002059 quaternary alloy Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1856—Phosphorus; Compounds thereof with iron group metals or platinum group metals with platinum group metals
-
- 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
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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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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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
- 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
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- 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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Abstract
A kind of platinum palladium nickel-phosphorus alloy porous nano elctro-catalyst and preparation method thereof of catalytic oxidation-reduction reaction, taking total volume respectively is the chloroplatinic acid and chlorine palladium acid sodium mixed solution of 4mL, then 0.01~0.2mL hydrochloric acid solution is added, add the F127 of 0.01~0.2g, finally add 1~10mL ascorbic acid solution, solution reacts under ultrasound after being sufficiently mixed, and is centrifugated, collects and precipitate and obtain after washing platinum-nickel alloys nanosphere, and precipitating is dispersed in again in 2mL aqueous solution；It takes volume to be added sequentially in platinum aqueous palladium for the sodium hypophosphite and 0.1~2mL nickel chloride solution of 0.2~5mL, 1~5mL sodium borohydride solution is then added, reaction is stirred at room temperature, obtain product after precipitating, milli-Q water, drying is collected by centrifugation.Operation of the present invention process is simple, and the reaction time is shorter, and material obtained has excellent electrocatalytic oxidation reducing property at normal temperatures and pressures.
Description
(1) technical field
The present invention relates to a kind of platinum palladium nickel-phosphorus alloy porous nano microballoons and preparation method thereof, which can be used for electrification
Learn the research of catalytic oxidation-reduction reaction.
(2) background technique
Oxygen reduction reaction is the key reaction that fuel battery negative pole occurs, and improves its kinetics with far reaching significance.
Currently, noble metal platinum is the elctro-catalyst of excellent catalytic oxidation-reduction reaction.However, metal platinum is expensive, reserves are low, hinder
The large-scale use of such catalyst.Therefore, novel platinum based catalyst is developed to accelerate the progress of oxygen reduction reaction, it is right
It all has a far reaching influence (Minhua Shao, Qiaowan Chang, Jean-Pol in the development of fuel cell and energy storage technology
Dodelet,Regis Chenitz.Recent Advances in Electrocatalysts for Oxygen
Reduction Reaction.Chem.Rev.2016,116,3594-3657)。
The composition and pattern of adjusting platinum based catalyst provide a kind of reliable method for the design of high performance catalyst.Mesh
Before, research relevant to porous platinum-base material is more.Compared with solid material, porous material specific surface area is bigger, catalytic activity
Site dramatically increases, thus shows more superior catalytic activity.Especially morphological rules, porous material of uniform size are reasons
Catalyst material (You Xu, the Bin Zhang.Recent Advances in Porous Pt-based thought
Nanostructures:Synthesis and Electrochemical Applications.Chem.Soc.Rev.2014,
43,2439-2450).Therefore, it is a feasible road that design novel porous materials, which carry out catalytic oxidation-reduction reaction,.
Alloy material based on platinum and transition metal is another catalyst material for being rich in potentiality.In such material platinum with
Its electronic structure can be adjusted by coordination and geometry effect between other metals, this is the superior basic reason of its catalytic performance
(Shaofang Fu,Chengzhou Zhu,Dan Du,Yuehe Lin.Enhanced Electrocatalytic
Activities of PtCuCoNi Three-Dimensional Nanoporous Quaternary Alloys for
Oxygen Reduction and Methanol Oxidation Reactions.ACS Appl.Mater.Interfaces
2016,8,6110-6116).In addition to traditional alloy material, in recent years studies have shown that by nonmetalloid (such as phosphorus, sulphur,
Boron) catalytic performance that can increase substantially platinum base alloy material is introduced into metal material.Further research shows non-
The valence electron of metallic element can improve the electronic structure of metal platinum, so as to improve its catalytic activity.Based on this, very polymeta-
Nonmetallic hybrid material is designed to be synthesized, and show better than conventional alloys material catalytic performance (Lili Zhang,
Meng Wei,Suqing Wang,Zhong Li,Liang-Xin Ding,Haihui Wang.Highly Stable PtP
Alloy Nanotube Arrays as a Catalyst for the Oxygen Reduction Reaction in
Acidic Medium.Chem.Sci.2015,6,3211–3216).However, that reports at present is mostly based on the miscellaneous of platinum and phosphorus
The synthetic method for changing material all uses higher phosphatization temperature and toxic reagent (such as positive tri octyl phosphine), is unfavorable for it further
Development.On the other hand, such material reported in the literature is mostly solid construction at present, and specific surface area is lower.Therefore, using simple
It is the key that exploitation high performance catalyst that feasible method design, which synthesizes porous platinum base hybrid material,.
(3) summary of the invention
It is an object of the present invention to provide a kind of platinum palladium nickel-phosphorus alloy porous nano microballoon of catalytic oxidation-reduction reaction and its preparations
Method, and catalytic oxidation-reduction reaction is studied.
The technical solution adopted by the present invention is that:
A kind of platinum palladium nickel-phosphorus alloy porous nano microballoon of catalytic oxidation-reduction reaction, prepares by the following method:
(1) match chloroplatinic acid, chlorine palladium acid sodium and nickel chloride solution of the concentration between 10~100mM respectively, concentration 1~
Hydrochloric acid solution between 10M, concentration is in 5~30mg mL-1Between sodium hypophosphite solution and concentration between 0.05~0.5M
Ascorbic acid and sodium borohydride solution；
(2) chloroplatinic acid and the mixing of chlorine palladium acid sodium that total volume is 4mL are taken respectively, and 0.01~0.2mL is then added and has prepared
Hydrochloric acid solution, add the F127 between 0.01~0.2g；The ascorbic acid solution of 1~10mL is finally added, mixing is equal
It is even；
(3) after solution is sufficiently mixed, heating water bath is placed in supersonic wave cleaning machine between 25~70 DEG C, reacts 1~6h
Afterwards, it is centrifugated, collects and precipitate and obtain after washing platinum-nickel alloys nanosphere, and precipitating is dispersed in 2mL aqueous solution again
In.
(4) volume is taken to be added sequentially to platinum palladium water for the sodium hypophosphite and 0.1~2mL nickel chloride solution of 0.2~5mL respectively
In solution, 1~5mL sodium borohydride solution is then added, reaction 20min is stirred at room temperature, precipitating is collected by centrifugation, with ultrapure washing
Wash, dry after obtain platinum palladium nickel-phosphorus alloy porous nano microballoon.
The selection of reaction condition is most important to the structure of the platinum palladium nickel-phosphorus alloy material of preparation.In the first stage, this hair
It is bright to select triblock copolymer F127 for structure directing agent, the reunion of nanoparticle can be effectively prevented, to obtain pattern rule
It is whole, finely dispersed nanostructure.In addition, ascorbic acid is as reducing agent, for the crystal knot of the platinum-nickel alloys material of synthesis
Its decisive role of structure.Wherein, the reproducibility of ascorbic acid is influenced by solution acid-basicity.Thus, proper volume is added
PH value of solution is adjusted in hydrochloric acid, is more advantageous to obtain the platinum nanometer Pd material with regular pattern.In second stage, it is with nickel chloride
Nickel source, Sodium Hypophosphite are phosphorus source, using sodium borohydride as reducing agent, are restored on platinum Pd nano particle surface, to having obtained
To the pattern of platinum palladium meso-porous nano microballoon do not influence.
A kind of preparation method of the platinum palladium nickel-phosphorus alloy porous nano microballoon of catalytic oxidation-reduction reaction, the method includes such as
Lower step:
(1) match chloroplatinic acid, chlorine palladium acid sodium and nickel chloride solution of the concentration between 10~100mM respectively, concentration 1~
Hydrochloric acid solution between 10M, concentration is in 5~30mg mL-1Between sodium hypophosphite solution and concentration between 0.05~0.5M
Ascorbic acid and sodium borohydride solution；
(2) chloroplatinic acid and the mixing of chlorine palladium acid sodium that total volume is 4mL are taken respectively, and 0.01~0.2mL is then added and has prepared
Hydrochloric acid solution, add the F127 between 0.01~0.2g；The ascorbic acid solution of 1~10mL is finally added, mixing is equal
It is even；
(3) after solution is sufficiently mixed, heating water bath is placed in supersonic wave cleaning machine between 25~70 DEG C, reacts 1~6h
Afterwards, it is centrifugated, collects and precipitate and obtain after washing platinum-nickel alloys nanosphere, and precipitating is dispersed in 2mL aqueous solution again
In.
(4) volume is taken to be added sequentially to platinum palladium water for the sodium hypophosphite and 0.1~2mL nickel chloride solution of 0.2~5mL respectively
In solution, 1~5mL sodium borohydride solution is then added, reaction 20min is stirred at room temperature, precipitating is collected by centrifugation, with ultrapure washing
Wash, dry after obtain platinum palladium nickel-phosphorus alloy porous nano microballoon.
Further, by controlling chloroplatinic acid, chlorine palladium acid sodium, the concentration and volume of hydrochloric acid and ascorbic acid, surfactant
Dosage, the additional amount of sodium hypophosphite, nickel chloride and sodium borohydride, and reaction temperature and time come control platinum palladium nickel phosphorus close
The pattern and structure of golden porous nano microballoon.
Electrochemical catalytic oxidation reduction reaction, specific performance test operating procedure are carried out at normal temperatures and pressures are as follows:
(1) catalyst ultrasonic dissolution obtained is configured to 1~5mg mL in ultrapure water-1Sample solution, use liquid relief
Pipe takes the sample solution of 1~10 μ L to drip in glassy carbon electrode surface, is placed on drying in 45 DEG C of baking ovens, then take the Nafion of 1~10 μ L
Solution (0.5wt%) is covered on catalyst surface, dry, obtains working electrode；Use platinum electrode as to electrode, Ag/ simultaneously
AgCl electrode carries out the test of electrocatalytic oxidation reducing property as reference electrode composition three-electrode system；
(2) perchloric acid solution that electrolyte used is 0.1M in test process, first leads to 30 points before hydrogen reduction performance test
The oxygen of clock is saturated its solution oxygen.The test program of cyclic voltammetry is first selected in testing, and 20 circle of scanning makes catalyst
Activation, then selects linear sweep voltammetry, sweeps the current conditions under speed in difference with computer monitor working electrode.Last root
Tafel slope, transfer electron number and hydrogen peroxide yield is calculated according to the data and corresponding formula that measure, for evaluating
The hydrogen reduction performance of catalyst.
The beneficial effects are mainly reflected as follows:
(1) operating procedure is simple, and reaction condition is mild, is not involved with using and discharging for noxious material.It is prepared
Product morphology it is regular, size is uniform, and meso-porous nano microballoon yield is very high.
(2) by control surfactant the available platinum palladium meso-porous nano ball of dosage, by regulation nickel source, phosphorus source and
The additional amount of sodium borohydride can introduce nickel and phosphorus in mesoporous platinum palladium simultaneously, so that the performance in hydrogen reduction application is different.
(3) the platinum palladium nickel-phosphorus alloy porous nano elctro-catalyst synthesized presents brilliant activity in redox reaction
And stability, transition metal and nonmetalloid, which is added, as elctro-catalyst in platinum-base material has very high application prospect.
(4) Detailed description of the invention
Fig. 1 is that the SEM of 1 platinum palladium nickel-phosphorus alloy porous nano microballoon of specific embodiments of the present invention schemes.
Fig. 2 is that TEM, HRTEM of 1 platinum palladium nickel-phosphorus alloy porous nano microballoon of specific embodiments of the present invention and Fourier become
Change figure.
Fig. 3 is the XRD diagram of 1 platinum palladium nickel-phosphorus alloy porous nano microballoon of specific embodiments of the present invention.
Fig. 4 is the XPS figure of different elements in 1 platinum palladium nickel-phosphorus alloy porous nano microballoon of specific embodiments of the present invention.
Fig. 5 is linear scan of the 1 platinum palladium nickel-phosphorus alloy porous nano microballoon of specific embodiments of the present invention under 1600 turns
Linear sweep voltammetry curve and transfer electron number under volt-ampere curve, Tafel slope figure, different rotating speeds.
Fig. 6 is 1 platinum palladium nickel-phosphorus alloy porous nano microballoon Rotation ring disk electrode electric current of specific embodiments of the present invention, transfer electronics
Several and hydrogen peroxide yield figure, linear sweep voltammetry curve and polarogram current-time curvel figure before and after 5000 circles.
Fig. 7 is that the SEM of 2 platinum palladium-nickel alloy porous nano microballoon of specific embodiments of the present invention schemes.
Fig. 8 is that the TEM of 2 platinum palladium-nickel alloy porous nano microballoon of specific embodiments of the present invention schemes.
Fig. 9 is linear scan volt of the 2 platinum palladium-nickel alloy porous nano microballoon of specific embodiments of the present invention under 1600 turns
Pacify curve and Tafel slope.
(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. 9, in the present embodiment, the redox performance test to the platinum palladium nickel nano material be
It is carried out on CHI 852D electrochemical workstation, operating process are as follows:
Catalyst ultrasonic dissolution obtained is configured to 2mg mL by the first step in ultrapure water-1Sample solution, use liquid relief
Pipe takes the sample solution of 5 μ L to drip in glassy carbon electrode surface, is placed on drying in 45 DEG C of baking ovens, then take the Nafion solution of 5 μ L
(0.5wt%) is covered on catalyst surface, dry, obtains working electrode；Use platinum electrode as to electrode, Ag/AgCl simultaneously
Electrode carries out the test of electrocatalytic oxidation reducing property as reference electrode composition three-electrode system；
Electrolyte used is the perchloric acid solution of 0.1M in second step, test process, is first led to before hydrogen reduction performance test
30 minutes oxygen is saturated its solution oxygen.The test program of cyclic voltammetry is first selected in testing, and 20 circle of scanning makes to urge
Agent activation, then selects linear sweep voltammetry, sweeps the current conditions under speed in difference with computer monitor working electrode.Most
Tafel slope, transfer electron number and hydrogen peroxide yield is calculated according to the data and corresponding formula that measure afterwards, is used to
Evaluate the hydrogen reduction performance of catalyst.
Embodiment 1
A kind of preparation method of the platinum palladium nickel-phosphorus alloy porous nano microballoon of catalytic oxidation-reduction reaction, the method includes such as
Lower step:
(1) chloroplatinic acid, chlorine palladium acid sodium and the nickel chloride solution for being respectively 20mM with concentration, concentration are the hydrochloric acid solution of 6M,
Concentration is 15mg mL-1Sodium hypophosphite solution and concentration be 0.1M ascorbic acid and sodium borohydride solution；
(2) the chlorine palladium acid sodium solution mixing for taking the chloroplatinic acid and 1mL of 3mL respectively, is then added the salt that 0.05mL has been prepared
Acid solution adds the F127 of 0.04g；The ascorbic acid solution of 4mL is finally added, is uniformly mixed；
(3) after solution is sufficiently mixed, it is placed in supersonic wave cleaning machine heating water bath to 40 DEG C, after reacting 4h, centrifuge separation,
It collects and precipitates and obtain after washing platinum-nickel alloys nanosphere, and precipitating is dispersed in again in 2mL aqueous solution.
(4) sodium hypophosphite and 0.4mL nickel chloride solution for taking 1mL respectively are added sequentially in platinum aqueous palladium, then plus
Enter 2mL sodium borohydride solution, be stirred at room temperature reaction 20min, be collected by centrifugation precipitating, with milli-Q water, dry after obtain platinum palladium
Nickel-phosphorus alloy porous nano microballoon.
The SEM figure of the platinum palladium nickel-phosphorus alloy porous nano microballoon of acquisition is referring to Fig. 1.The platinum palladium nickel-phosphorus alloy of acquisition is porous to be received
TEM, HRTEM and Fourier transformation figure of meter Wei Qiu is referring to fig. 2.The XRD diagram of the platinum palladium nickel-phosphorus alloy porous nano microballoon of acquisition
Referring to Fig. 3.The XPS figure of the platinum palladium nickel-phosphorus alloy porous nano microballoon difference element of acquisition is referring to fig. 4.The platinum palladium nickel phosphorus of acquisition closes
Golden porous nano microballoon is in the linear sweep voltammetry curve under 1600 turns, Tafel slope figure, the linear scan under different rotating speeds
Volt-ampere curve and transfer electron number are referring to Fig. 5.Platinum palladium nickel-phosphorus alloy porous nano microballoon Rotation ring disk electrode electric current, the transfer electricity of acquisition
Subnumber and hydrogen peroxide yield figure, the linear sweep voltammetry curve before and after 5000 circles and polarogram current-time curvel figure are referring to figure
6。
It can be seen that by SEM figure, obtained platinum palladium nickel phosphorus is spherical mesoporous structure, in particle surface it can be seen that equally distributed
Duct, and particle size is uniform, platinum palladium nickel phosphorus porous nano microballoon yield is close to 100%.TEM figure can further confirm its Jie
Pore structure, and the branch of mutually commissure extends to inside particles, increases particle specific surface area and active site, more
Be conducive to the promotion of electrocatalysis characteristic.By HRTEM, electronic diffraction ring and XRD analysis, product is polycrystalline structure.By XRD and
XPS analysis, platinum palladium nickel phosphorus porous nanoparticles form alloy structure.It can be seen that platinum palladium nickel by linear sweep voltammetry curve
Phosphorus porous nano particle has the take-off potential (1.000V vs.RHE) and half wave potential (0.934V of very positive catalytic oxidation-reduction
vs.RHE).Can be calculated Tafel slope by linear sweep voltammetry curve is 61.2mV dec-1, it was demonstrated that during hydrogen reduction
The transfer of first electronics is rate determining step.Pass through the linear sweep voltammetry curve and transfer electron number under different rotating speeds, rotation
Change disk electric current, shifting electron number and hydrogen peroxide yield can be seen that and four electron reactions have occurred during hydrogen reduction, and
And intermediate product is seldom.It can be seen that from the linear sweep voltammetry curve comparison and polarogram current-time curvel of 5000 circle front and backs
Platinum palladium nickel phosphorus porous nano particle has good stability.
Embodiment 2
A kind of preparation method of the platinum palladium nickel-phosphorus alloy porous nano microballoon of catalytic oxidation-reduction reaction, the method includes such as
Lower step:
(1) respectively with concentration be 20mM chloroplatinic acid, chlorine palladium acid sodium and nickel chloride solution, concentration be 6M hydrochloric acid solution and
Concentration is the ascorbic acid and sodium borohydride solution of 0.1M；
(2) the chlorine palladium acid sodium solution mixing for taking the chloroplatinic acid and 1mL of 3mL respectively, is then added the salt that 0.05mL has been prepared
Acid solution adds the F127 of 0.04g；The ascorbic acid solution of 4mL is finally added, is uniformly mixed；
(3) after solution is sufficiently mixed, it is placed in supersonic wave cleaning machine heating water bath to 40 DEG C, after reacting 4h, centrifuge separation,
It collects and precipitates and obtain after washing platinum-nickel alloys nanosphere, and precipitating is dispersed in again in 2mL aqueous solution.
(4) it takes 0.4mL nickel chloride solution to be added in platinum aqueous palladium, 2mL sodium borohydride solution is then added, room temperature is stirred
Mix reaction 20min, be collected by centrifugation precipitating, with milli-Q water, dry after obtain platinum palladium nickel porous nano microballoon.
It can be seen that by SEM and TEM figure, platinum palladium nickel porous nano microballoon is formed, when showing that only nickel source is added and lacks phosphorus source
The mesoporous pattern of particle can still be kept.It can be seen that platinum palladium nickel porous nano microballoon by linear sweep voltammetry curve and be catalyzed oxygen
The take-off potential (0.987V vs.RHE) and half wave potential (0.909V vs.RHE) of reduction are in the position of calibration.According to linear
It is 67.3mV dec that scanning volt-ampere curve, which can be calculated Tafel slope,-1, it was demonstrated that the first electronics turns during hydrogen reduction
Shifting is rate determining step.
Embodiment 3
A kind of preparation method of the platinum palladium nickel-phosphorus alloy porous nano microballoon of catalytic oxidation-reduction reaction, the method includes such as
Lower step:
(1) chloroplatinic acid, chlorine palladium acid sodium and the nickel chloride solution for being respectively 10mM with concentration, concentration are the hydrochloric acid solution of 1M,
Concentration is 5mg mL-1Sodium hypophosphite solution and concentration be 0.05M ascorbic acid and sodium borohydride solution；
(2) the chlorine palladium acid sodium solution mixing for taking the chloroplatinic acid and 1mL of 3mL respectively, is then added the salt that 0.01mL has been prepared
Acid solution adds the F127 of 0.01g；The ascorbic acid solution of 1mL is finally added, is uniformly mixed；
(3) after solution is sufficiently mixed, it is placed in supersonic wave cleaning machine heating water bath to 25 DEG C, after reacting 1h, centrifuge separation,
It collects and precipitates and obtain after washing platinum-nickel alloys nanosphere, and precipitating is dispersed in again in 2mL aqueous solution.
(4) sodium hypophosphite and 0.1mL nickel chloride solution for taking 0.2mL respectively are added sequentially in platinum aqueous palladium, then
Be added 1mL sodium borohydride solution, be stirred at room temperature reaction 20min, be collected by centrifugation precipitating, with milli-Q water, dry after obtain platinum
Palladium nickel-phosphorus alloy porous nano microballoon.
Since in this reaction process, the concentration of chloroplatinic acid, chlorine palladium acid sodium and ascorbic acid is very low, therefore restores
Metal precursor it is seldom, be difficult to be centrifuged out from solution, the amount of F127 is also fewer, be difficult regulate and control catalyst pattern,
Moreover, reaction temperature is relatively low, reduction effect is also undesirable.Further, the additional amount of nickel source and phosphorus source is all lower, adulterates effect
Also undesirable.It is therefore more difficult to prepare platinum palladium nickel phosphorus porous nano microballoon as expected.
Embodiment 4
A kind of preparation method of the platinum palladium nickel-phosphorus alloy porous nano microballoon of catalytic oxidation-reduction reaction, the method includes such as
Lower step:
(1) chloroplatinic acid, chlorine palladium acid sodium and the nickel chloride solution for being respectively 100mM with concentration, concentration are that the hydrochloric acid of 10M is molten
Liquid, concentration are 30mg mL-1Sodium hypophosphite solution and concentration be 0.5M ascorbic acid and sodium borohydride solution；
(2) the chlorine palladium acid sodium solution mixing for taking the chloroplatinic acid and 1mL of 3mL respectively, is then added the hydrochloric acid that 0.2mL has been prepared
Solution adds the F127 of 0.2g；The ascorbic acid solution of 10mL is finally added, is uniformly mixed；
(3) after solution is sufficiently mixed, it is placed in supersonic wave cleaning machine heating water bath to 70 DEG C, after reacting 6h, centrifuge separation,
It collects and precipitates and obtain after washing platinum-nickel alloys nanosphere, and precipitating is dispersed in again in 2mL aqueous solution.
(4) sodium hypophosphite and 2mL nickel chloride solution for taking 5mL respectively are added sequentially in platinum aqueous palladium, are then added
5mL sodium borohydride solution, be stirred at room temperature reaction 20min, be collected by centrifugation precipitating, with milli-Q water, dry after obtain platinum palladium nickel
Phosphorus alloy porous nano microballoon.
In first step reaction, the concentration of chloroplatinic acid, chlorine palladium acid sodium and ascorbic acid is higher, and reaction rate is more difficult to control；
The additional amount of hydrochloric acid is higher, and Ascorbic Acid reaction rate is affected, and simultaneous reactions temperature is excessively high, is unfavorable for meso-hole structure
It is formed.In step (4), the additional amount of sodium hypophosphite, nickel chloride and sodium borohydride is very high, keeps the rate of reduction of phosphorus and nickel aobvious
It writes and increases, nickel source and phosphorus source cannot be adulterated well into platinum-nickel alloys material, therefore the more difficult ideal platinum palladium nickel phosphorus of synthesis
Alloy nano-material.
Claims (3)
1. a kind of platinum palladium nickel-phosphorus alloy porous nano microballoon of catalytic oxidation-reduction reaction, prepares by the following method:
(1) respectively match chloroplatinic acid, chlorine palladium acid sodium and nickel chloride solution of the concentration between 10~100mM, concentration 1~10M it
Between hydrochloric acid solution, concentration is in 5~30mg mL-1Between sodium hypophosphite solution and concentration it is anti-bad between 0.05~0.5M
Hematic acid and sodium borohydride solution；
(2) chloroplatinic acid and the mixing of chlorine palladium acid sodium that total volume is 4mL are taken respectively, and the salt that 0.01~0.2mL has been prepared then is added
Acid solution adds the F127 between 0.01~0.2g；The ascorbic acid solution of 1~10mL is finally added, is uniformly mixed；
(3) after solution is sufficiently mixed, it is placed in supersonic wave cleaning machine heating water bath between 25~70 DEG C, after reacting 1~6h, from
Heart separation collects and precipitates and obtain after washing platinum-nickel alloys nanosphere, and precipitating is dispersed in again in 2mL aqueous solution.
(4) volume is taken to be added sequentially to platinum aqueous palladium for the sodium hypophosphite and 0.1~2mL nickel chloride solution of 0.2~5mL respectively
In, 1~5mL sodium borohydride solution is then added, reaction 20min is stirred at room temperature, precipitating is collected by centrifugation, with milli-Q water, dry
Platinum palladium nickel-phosphorus alloy porous nano microballoon is obtained after dry.
2. a kind of preparation side of the platinum palladium nickel-phosphorus alloy porous nano microballoon of catalytic oxidation-reduction reaction as described in claim 1
Method, which is characterized in that described method includes following steps:
(1) respectively match chloroplatinic acid, chlorine palladium acid sodium and nickel chloride solution of the concentration between 10~100mM, concentration 1~10M it
Between hydrochloric acid solution, concentration is in 5~30mg mL-1Between sodium hypophosphite solution and concentration it is anti-bad between 0.05~0.5M
Hematic acid and sodium borohydride solution；
(2) chloroplatinic acid and the mixing of chlorine palladium acid sodium that total volume is 4mL are taken respectively, and the salt that 0.01~0.2mL has been prepared then is added
Acid solution adds the F127 between 0.01~0.2g；The ascorbic acid solution of 1~10mL is finally added, is uniformly mixed；
(3) after solution is sufficiently mixed, it is placed in supersonic wave cleaning machine heating water bath between 25~70 DEG C, after reacting 1~6h, from
Heart separation collects and precipitates and obtain after washing platinum-nickel alloys nanosphere, and precipitating is dispersed in again in 2mL aqueous solution.
(4) volume is taken to be added sequentially to platinum aqueous palladium for the sodium hypophosphite and 0.1~2mL nickel chloride solution of 0.2~5mL respectively
In, 1~5mL sodium borohydride solution is then added, reaction 20min is stirred at room temperature, precipitating is collected by centrifugation, with milli-Q water, dry
Platinum palladium nickel-phosphorus alloy porous nano microballoon is obtained after dry.
3. method according to claim 2, which is characterized in that pass through control chloroplatinic acid, chlorine palladium acid sodium, hydrochloric acid and ascorbic acid
Concentration and volume, the dosage of surfactant, the additional amount of sodium hypophosphite, nickel chloride and sodium borohydride, and reaction temperature
Degree and time control the pattern and structure of platinum palladium nickel-phosphorus alloy porous nano microballoon.
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