CN108187693A - One pot of method without the hot method synthesis PtCu hollow Nano cage materials of templating solvent - Google Patents
One pot of method without the hot method synthesis PtCu hollow Nano cage materials of templating solvent Download PDFInfo
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- CN108187693A CN108187693A CN201810039504.2A CN201810039504A CN108187693A CN 108187693 A CN108187693 A CN 108187693A CN 201810039504 A CN201810039504 A CN 201810039504A CN 108187693 A CN108187693 A CN 108187693A
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- 239000000463 material Substances 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000002091 nanocage Substances 0.000 title claims abstract description 15
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 14
- 239000002904 solvent Substances 0.000 title claims abstract description 14
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 13
- 238000005580 one pot reaction Methods 0.000 title claims abstract description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 72
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 36
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 16
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 239000004475 Arginine Substances 0.000 claims abstract description 9
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 9
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 8
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims abstract description 7
- 230000003647 oxidation Effects 0.000 claims abstract description 6
- 241000549556 Nanos Species 0.000 claims abstract description 4
- 238000005119 centrifugation Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 230000009467 reduction Effects 0.000 claims description 8
- 239000010949 copper Chemical group 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 6
- 230000009471 action Effects 0.000 claims description 6
- 238000010276 construction Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 230000007797 corrosion Effects 0.000 claims description 3
- 238000005260 corrosion Methods 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 12
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 abstract description 10
- 235000011187 glycerol Nutrition 0.000 abstract description 5
- 239000002086 nanomaterial Substances 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract description 3
- 238000006479 redox reaction Methods 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 12
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 241000872198 Serjania polyphylla Species 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000011943 nanocatalyst Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
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- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- DWNBOPVKNPVNQG-LURJTMIESA-N (2s)-4-hydroxy-2-(propylamino)butanoic acid Chemical compound CCCN[C@H](C(O)=O)CCO DWNBOPVKNPVNQG-LURJTMIESA-N 0.000 description 1
- VEJOYRPGKZZTJW-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;platinum Chemical compound [Pt].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O VEJOYRPGKZZTJW-FDGPNNRMSA-N 0.000 description 1
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Chemical group OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ODKSFYDXXFIFQN-BYPYZUCNSA-P L-argininium(2+) Chemical compound NC(=[NH2+])NCCC[C@H]([NH3+])C(O)=O ODKSFYDXXFIFQN-BYPYZUCNSA-P 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical group OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000637 arginyl group Chemical group N[C@@H](CCCNC(N)=N)C(=O)* 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
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- 238000000970 chrono-amperometry Methods 0.000 description 1
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- 230000005494 condensation Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
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- 229940008099 dimethicone Drugs 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- JZZIHCLFHIXETF-UHFFFAOYSA-N dimethylsilicon Chemical compound C[Si]C JZZIHCLFHIXETF-UHFFFAOYSA-N 0.000 description 1
- 238000011549 displacement method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
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- 238000011049 filling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000004220 glutamic acid Chemical group 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 description 1
- 125000000487 histidyl group Chemical group [H]N([H])C(C(=O)O*)C([H])([H])C1=C([H])N([H])C([H])=N1 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000007040 multi-step synthesis reaction Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- -1 oleyl amines Chemical class 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
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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
- 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
- B01J23/8926—Copper and noble metals
-
- B01J35/40—
Abstract
The invention discloses one pot of methods without the hot method synthesis PtCu hollow Nano cage materials of templating solvent, belong to the synthesis technical field of cage-shaped nano material.Technical scheme of the present invention main points are：Pattern directed agents hexadecyltrimethylammonium chloride, metal precursor acetylacetone,2,4-pentanedione platinum are placed in reaction vessel and are uniformly mixed with copper chloride, reducing agent arginine and solvent oleyl amine, obtained mixing material is placed in oil bath pan again and is heated to 160 DEG C of reaction 8h, is cooled to room temperature centrifugation after reaction, washing, drying obtain PtCu hollow Nano cage materials.Preparation process of the present invention is simple and convenient and easily controllable, and PtCu hollow Nanos cage material obtained is significantly increased to the catalytic activity and stability of redox reactions, oxidation of glycol reaction and glycerine oxidation reaction.
Description
Technical field
The invention belongs to the synthesis technical fields of cage-shaped nano material, and in particular to one pot without the hot method synthesis of templating solvent
PtCu hollow Nano cages（PtCu NCs）The method of material.
Background technology
With explosive population growth and a large amount of consumption of fossil energy, the whole world all suffers from the dual of energy crisis and environmental pollution
Pressure, fuel cell are just being increasingly subject to the concern of people as a kind of clean energy substitution technology.It is urged in fuel battery negative pole
Change in application, platinum（Pt）Catalyst is most efficient single-metal reforming catalyst.However the high price of Pt, low cathodic oxygen reduction are active and low
The factors such as anti-CO toxicity limit its large-scale business application.Therefore the dosage for how reducing Pt improves its cathode oxygen and urges simultaneously
Change activity with stability as one of key scientific problems in catalytic base scientific research.
Up to the present, most of research is concentrated mainly on the modification to pure Pt catalyst and direction of modification.On the one hand it is
Its quality specific activity is improved, mainly adulterates to form Pt-M by non-noble metal j element（M=Cu, Ni, Co etc.）Bimetallic alloy is catalyzed
Agent regulates and controls the electronic structure of Pt to promote the catalytic effect of catalyst while Pt contents in reducing catalyst, can also lead to
Distribution of the regulation and control each element component in nano particle is crossed to improve its performance.On the other hand it is then to increase specific surface area active,
The utilization rate of Pt is effectively improved by building the means such as three-D space structure, the pattern for regulating and controlling nanocatalyst and size.Mesh
Before until, the nano material that controlledly synthesis has specific morphology component is in progress, and shows that Pt dosages are few, and performance is good
Etc. various advantages.However, this kind of catalyst would generally undergo asking for sintering, reunion and transition metal dissolution in use
Topic, material morphology is caused to develop to be reduced with persistence.Therefore, seek balance between the activity of nanocatalyst and stability still
It is so a huge challenge.
For this problem, researcher is directed generally to develop miscellaneous synthesis strategy and goes to prepare high activity high stable
Property polycrystalline Pt-M nanocages, these synthetic methods mainly have seed mediated growth method, electrochemical displacement method, sacrifice template etc..No
It is mostly multistep structure to cross these prior synthesizing methods, and building-up process is complicated, and elapsed time is long, therefore builds nanometer by one kettle way
Cage is always the difficult point of researcher's research.
Invention content
The present invention provides a kind of system to overcome the problems, such as that multistep synthesis metal nano cage material exists in the prior art
The simple one pot of controllable method without the hot method synthesis PtCu hollow Nano cage materials of templating solvent of standby process, made from this method
PtCu hollow Nano cage materials are to redox reactions（ORR）, oxidation of glycol reaction（EGOR）With glycerine oxidation reaction
（GOR）Catalytic activity and stability be significantly increased.
The present invention adopts the following technical scheme that one pot empty without the hot method synthesis PtCu of templating solvent to solve above-mentioned technical problem
The method of heart nanocages material, it is characterised in that the specific steps are：By pattern directed agents hexadecyltrimethylammonium chloride
（CTAC）, metal precursor acetylacetone,2,4-pentanedione platinum（Pt(acac)2）With copper chloride（CuCl2·2H2O）, reducing agent arginine and solvent
Oleyl amine is placed in reaction vessel and is uniformly mixed, wherein the molar concentration of hexadecyltrimethylammonium chloride be 20mM, levulinic
The molar concentration of ketone platinum is 5mM, and the molar concentration of copper chloride is 5mM, and arginic molar concentration is 60mM, then mixed by what is obtained
Condensation material, which is placed in oil bath pan, is heated to 160 DEG C of reaction 8h, is cooled to room temperature centrifugation after reaction, washing, drying obtain
PtCu hollow Nano cage materials.
Further preferably, the average grain diameter of PtCu hollow Nanos cage material obtained is 11.2nm, and hollow out skeleton is averaged
Thickness is 2.09nm, and the detailed process that hollow Nano basket structure is formed is：Metal precursor acetylacetone,2,4-pentanedione platinum and copper chloride are also
Pt atoms and Cu atoms are formed under the common reduction of former agent arginine and solvent oleyl amine, it is final to live through potential reduction deposition
PtCu cores are formed, under the action of pattern directed agents hexadecyltrimethylammonium chloride, PtCu cores selectivity is along edge { 110 }
Special crystal face is to extension, and after undergoing the reaction time of 4h, PtCu karyomorphisms are into indent solid construction, as the reaction time extends,
In oxidation corrosion agent Cl-/O2Under the action of indent solid construction gradually by oxide etch into hollow porous structure, ultimately generate sky
Heart nanometer basket structure.
Compared with the prior art, the present invention has the following advantages：The PtCu hollow Nano cages material of the present invention uses one pot of nothing
The hot method of templating solvent is prepared, and does not need to pre-synthesis template, and a step prepares hollow-core construction, and process is simple and convenient, is easy to control
System, compared to business Pt/C（50wt.%）With the black nano materials of Pt, PtCu hollow Nanos cage material produced by the present invention is to oxygen
Reduction reaction（ORR）, oxidation of glycol reaction（EGOR）With glycerine oxidation reaction（GOR）Catalytic activity and stability have
It significantly improves.
Description of the drawings
Fig. 1 is the transmission electron microscope picture of PtCu NCs materials and angle of elevation annular dark field scanning transmission electron microscope figure, inserting in wherein B
Figure is its structural model, and circle represents atom ladder in C, and arrow meaning represents high miller index surface；
Fig. 2 is the power spectrum of PtCu NCs materials（EDX）, X-ray diffraction（XRD）And x-ray photoelectron spectroscopy（XPS）Figure；
Fig. 3 is the transmission electron microscope picture of the PtCu NCs materials under differential responses time conditions, and wherein A is 2h, B 4h, C 6h, D
For 8h, E is PtCu NCs material formation process schematic diagrames；
A is PtCu NCs, Pt/C and the black cyclic voltammetrics in 0.5M KOH solutions of Pt in Fig. 4（CV）Curve, B PtCu
The black ORR polarization curves in oxygen-saturated 0.5M KOH solutions of NCs, Pt/C and Pt, C and D are in 0.90V（vs.RHE）
Front and rear mass activity is enclosed in scan round 1000 under current potential（C）With it is area activated（D）；
A and C is black in 0.5M KOH solutions for PtCu NCs, Pt/C and Pt in Fig. 5（Ethylene glycol containing 0.5M and glycerine respectively）'s
CV schemes, and B and D are corresponding If/Ib（IfAnd IbForward and reverse peak current density is represented respectively）, wherein A and B correspond to EGOR, C
GOR is corresponded to D；
A and C is PtCu NCs, Pt/C and the black mass activities to EGOR and GOR of Pt and area activated in Fig. 6, and B and D are corresponding
Chronoa mperometric plot, wherein A and B correspond to EGOR, C and D and correspond to GOR.
Specific real-time mode
The above of the present invention is described in further details by the following examples, but this should not be interpreted as to the present invention
The range of above-mentioned theme is only limitted to following embodiment, and all technologies realized based on the above of the present invention belong to the present invention's
Range.
Embodiment 1
Reagent and instrument
Hexadecyltrimethylammonium chloride, acetylacetone,2,4-pentanedione platinum, copper chloride（CuCl2·2H2O）, arginine, oleyl amine, dimethyl-silicon
Oil, ethyl alcohol, hexamethylene buy Shanghai Chemical Plant, and all reagents are that analysis is pure.Scanning electron microscope（SEM, JSM-
6390LV, JEOL, Japan）, transmission electron microscope（TEM, JEM-2100, JEOL, Japan）, accelerating potential 200kV.
The chemical composition of PtCu NCs materials is by energy disperse spectroscopy（EDX, Oxford）, X-ray diffraction（XRD）It determines, the change of Pt and Cu
Valence state is learned by x-ray photoelectron spectroscopy（XPS）It determines.
By pattern directed agents hexadecyltrimethylammonium chloride, metal precursor acetylacetone,2,4-pentanedione platinum and copper chloride（CuCl2·
2H2O）It is placed in the reaction vessel for filling 5mL solvent oleyl amines with reducing agent arginine and ultrasonic mixing is uniform, wherein cetyl
The molar concentration of trimethyl ammonium chloride is 20mM, and the molar concentration of acetylacetone,2,4-pentanedione platinum is 5mM, and the molar concentration of copper chloride is 5mM,
Arginic molar concentration is 60mM, then obtained mixed solution is placed in oil bath pan（Dimethicone）In be heated to 160 DEG C
8h is reacted, is cooled to room temperature centrifugation after reaction, washing, drying obtain PtCu NCs materials, used detergent is body
Product ratio 9:1 ethyl alcohol and the mixed solution of hexamethylene.
Fig. 1 is the transmission electron microscope picture of PtCu NCs materials and angle of elevation annular dark field scanning transmission electron microscope figure.As seen from the figure
PtCu NCs materials are hollow porous three-dimensional cage structures, and average grain diameter 11.2nm, edge thickness is about 2.09nm, and
There are a large amount of lattice defects and high miller index surfaces for body structure surface, this is conducive to provide abundant active site for catalysis reaction.By
D in Fig. 1 is it is found that Pt elements and Cu Elemental redistributions are uniform, it was demonstrated that PtCu NCs materials form alloy structure.The illustration of C in Fig. 1
Selective electron diffraction figure illustrates its polycrystalline essence.
Fig. 2 is the power spectrum of PtCu NCs materials（EDX）, X-ray diffraction（XRD）And x-ray photoelectron spectroscopy（XPS）
Figure.In Fig. 2 A EDS the result shows that Pt/Cu atomic ratios in PtCu NCs materials for B in 49/51, Fig. 2 XRD results into one
Step illustrates that the PtCu NCs materials are alloy structures, and the XPS results of C-D illustrate metal precursor Pt (acac) in Fig. 22With
CuCl2·2H2O is effectively reduced to Pt atoms and Cu atoms.
Fig. 3 is that the intermediate product obtained by the differential responses time explains the growth mechanism of PtCu NCs materials, the growth
Mechanism may be interpreted as nucleation, three step of selective growth and oxide etch.Metal precursor Pt (acac)2And CuCl2·2H2O is in essence
Pt atoms and Cu atoms are formed under the common reduction of propylhomoserin and oleyl amine, potential reduction is lived through and deposits to form PtCu cores, in pattern
Under the action of directed agents CTAC, PtCu cores selectivity, to extension, undergoes the reaction time of 4h along edge { 110 } special crystal face
Afterwards, PtCu karyomorphisms are into indent solid construction, as the reaction time extends, in oxidation corrosion agent Cl-/O2Under the action of indent it is solid
Structure ultimately generates hollow Nano basket structure gradually by oxide etch into hollow porous structure.
Fig. 4-6 be under alkaline condition PtCu NCs materials to the catalytic applications of ORR, EGOR and GOR.
A is PtCu NCs, Pt/C and the black CV figures in 0.5M KOH solutions of Pt in Fig. 4, according to liberation of hydrogen dehydrogenation part
（0.1-0.4）V is calculated, the electrochemical surface area of PtCu NCs（EASA）It is 19.8m2g–1 PtThough less than the Pt/C of business,
It is more black than Pt（Grain size about 8nm）Greatly, this must be attributed to the fact that the hollow porous immanent structure of PtCu NCs materials.PtCu NCs materials
Larger EASA demonstrates on its surface that there are abundant electro-chemical activity sites, it can promote gas diffusion and electron transmission,
So as to improve the catalytic performance of material.B is that PtCu NCs, Pt/C and Pt are black in oxygen-saturated 0.5M KOH solutions in Fig. 4
ORR polarization curves, rotating speed 1600rpm sweep speed as 10mVs–1.PtCu NCs materials play spike potential（1.02V）, than business
Pt/C（0.97V）It is black with Pt（0.93V）Corrigendum, has reacted the efficient catalytic activity of PtCu NCs materials.In addition to this, C in Fig. 3
The front and rear mass activity in 0.90V of 1000 circle of PtCu NCs material circulations scanning and area activated is illustrated with D（It is marked respectively
Standard turns to the load capacity and EASA of Pt）, mass activity（1.28Amg–1 Pt）With it is area activated（6.46mAcm–2 EASA）More than Pt/
C（0.43Amg–1 Pt, 0.88mAcm–2 EASA）It is black with Pt（0.074Amg–1 Pt, 0.48mAcm–2 EASA）, this result further demonstrates that
PtCu NCs materials have efficient electrocatalysis characteristic.In addition, it lives with reference to the mass activity and area that above-mentioned material the 1000th encloses
Property it is found that accelerated stability test（ADT）Afterwards, mass activity and area activated reduction of the PtCu NCs materials in 0.90V
15.4%, less than Pt/C（69.0%）It is black with Pt（65.1%）, the result demonstrate PtCu NCs materials have to ORR it is good steady
It is qualitative.
Fig. 5 be PtCu NCs materials under alkaline condition（0.5M KOH solutions）The CV of EGOR and GOR is schemed.It is urged identical
Under conditions of agent amount, compared with control material, the current density highest of PtCu NCs materials respectively reaches EGOR and GOR
111.43mAcm–2And 134.54mAcm–2, and its If/IbMaximum, this shows that PtCu NCs materials have in stronger anti-CO
Malicious ability.
Fig. 6 intuitively discloses catalytic activity and stability of the PtCu NCs materials in EGOR and GOR tests.PtCu
The mass activity of NCs materials（EGOR and GOR is 2.65Amg respectively–1 PtAnd 3.19Amg–1 Pt）With it is area activated（EGOR and GOR points
It is not 13.40mAcm–2 EASAAnd 16.08mAcm–2 EASA）Black much larger than control material Pt/C and Pt, this also demonstrates PtCu NCs
Material is to the efficient catalytic ability of ethylene glycol and glycerine.C and D is that PtCu NCs materials are right in 0.5M KOH solutions in Fig. 6
The stability test of EGOR and GOR, under the current potential of 0.70V, after testing 10000s by chronoamperometry, PtCu NCs materials
Current density be kept at 4.0mA cm–2With 7.8mA cm–2, more than Pt/C（0.6mAcm–2With 1.36mA cm–2）And Pt
It is black（0.5mAcm–2And 0.3mAcm–2）, this demonstrates again that PtCu NCs materials have excellent catalytic performance and persistently steady
It is qualitative.
Embodiment 2
In the present embodiment, reducing agent arginine concentrations change（30mM, 80mM）, other experiment conditions reference embodiments 1,
It remains unchanged, the PtCu NPs materials being prepared are shown in backing material, and hollow porous structure disappears, and particle uniformity becomes
Difference, polymerize between particle serious, and grain size becomes larger.
Embodiment 3
In the present embodiment, arginine is substituted with histidine and glutamic acid respectively, other experiment conditions are kept with reference to embodiment 1
Constant, the PtCu NPs materials being prepared are shown in backing material, and hollow porous pattern disappears, and becomes solid irregular
Grain.
According to embodiment 1-3 it is found that during hollow Nano basket structure is generated reducing agent concentration, the type of reducing agent
And the reaction time is all vital.
Basic principle, main features and advantages embodiment above describes the present invention, the technical staff of the industry should
Understand, the present invention is not limited to the above embodiments, and the above embodiments and description only describe the originals of the present invention
Reason, under the range for not departing from the principle of the invention, various changes and improvements may be made to the invention, these changes and improvements are each fallen within
In the scope of protection of the invention.
Claims (2)
1. one pot of method without the hot method synthesis PtCu hollow Nano cage materials of templating solvent, it is characterised in that the specific steps are：It will
Pattern directed agents hexadecyltrimethylammonium chloride, metal precursor acetylacetone,2,4-pentanedione platinum and copper chloride CuCl2·2H2O, reducing agent
Arginine and solvent oleyl amine are placed in reaction vessel and are uniformly mixed, and the molar concentration of wherein hexadecyltrimethylammonium chloride is
20mM, the molar concentration of acetylacetone,2,4-pentanedione platinum is 5mM, and the molar concentration of copper chloride is 5mM, and arginic molar concentration is 60mM,
Obtained mixing material is placed in oil bath pan again and is heated to 160 DEG C of reaction 8h, centrifugation is cooled to room temperature after reaction, washes
It washs, dry and obtain PtCu hollow Nano cage materials.
2. the one pot according to claim 1 method without the hot method synthesis PtCu hollow Nano cage materials of templating solvent, special
Sign is：The average grain diameter of PtCu hollow Nanos cage material obtained is 11.2nm, and the average thickness of hollow out skeleton is 2.09nm,
Hollow Nano basket structure formed detailed process be：Metal precursor acetylacetone,2,4-pentanedione platinum and copper chloride are in reducing agent arginine and molten
Pt atoms and Cu atoms are formed under the common reduction of agent oleyl amine, potential reduction deposition is lived through and ultimately forms PtCu cores,
Under the action of pattern directed agents hexadecyltrimethylammonium chloride, PtCu cores selectivity is outside along edge { 110 } special crystal face
Prolong and open, after undergoing the reaction time of 4h, PtCu karyomorphisms are into indent solid construction, as the reaction time extends, in oxidation corrosion agent
Cl-/O2Under the action of indent solid construction gradually by oxide etch into hollow porous structure, ultimately generate hollow Nano basket structure.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109256568A (en) * | 2018-08-16 | 2019-01-22 | 陕西师范大学 | Monodisperse, rich Pt nanocages material of wall thickness controllable precise and the preparation method and application thereof |
| CN111250008A (en) * | 2020-02-08 | 2020-06-09 | 浙江师范大学 | Method for synthesizing hollow sphere nano material formed by wrapping CoFe alloy in N and P co-doped carbon assembly by solvent-free thermal decomposition method |
| CN111987328A (en) * | 2020-08-17 | 2020-11-24 | 河南师范大学 | Preparation method of electrocatalyst with nanoparticle structure for methanol fuel cell |
| CN115188978A (en) * | 2022-08-05 | 2022-10-14 | 中国科学技术大学 | Preparation method and application of supported polycrystalline surface defect high-entropy alloy catalyst |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103350234A (en) * | 2013-07-05 | 2013-10-16 | 浙江大学 | Preparation method of platinum copper concave alloy nanometer crystal, and platinum copper concave alloy nanometer crystal prepared through preparation method of platinum copper concave alloy nanometer crystal |
| CN103402633A (en) * | 2011-01-20 | 2013-11-20 | 昭和电工株式会社 | Catalyst carrier production method, composite catalyst production method, composite catalyst, fuel cell using same |
| CN103696016A (en) * | 2013-11-27 | 2014-04-02 | 浙江大学 | Platinoid alloy nano dendritic crystal and preparation method thereof |
| CN104607652A (en) * | 2015-01-17 | 2015-05-13 | 南京师范大学 | Controllable precious metal nanocatalyst synthesis method with amino acid as soft templates |
| CN107442117A (en) * | 2017-06-16 | 2017-12-08 | 福州大学 | A kind of exhaust gas catalytic conversion |
-
2018
- 2018-01-16 CN CN201810039504.2A patent/CN108187693B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103402633A (en) * | 2011-01-20 | 2013-11-20 | 昭和电工株式会社 | Catalyst carrier production method, composite catalyst production method, composite catalyst, fuel cell using same |
| CN103350234A (en) * | 2013-07-05 | 2013-10-16 | 浙江大学 | Preparation method of platinum copper concave alloy nanometer crystal, and platinum copper concave alloy nanometer crystal prepared through preparation method of platinum copper concave alloy nanometer crystal |
| CN103696016A (en) * | 2013-11-27 | 2014-04-02 | 浙江大学 | Platinoid alloy nano dendritic crystal and preparation method thereof |
| CN104607652A (en) * | 2015-01-17 | 2015-05-13 | 南京师范大学 | Controllable precious metal nanocatalyst synthesis method with amino acid as soft templates |
| CN107442117A (en) * | 2017-06-16 | 2017-12-08 | 福州大学 | A kind of exhaust gas catalytic conversion |
Non-Patent Citations (2)
| Title |
|---|
| SHUIPING LUO ET AL.: "Concave Platinum−Copper Octopod Nanoframes Bounded with Multiple High-Index Facets for Efficient Electrooxidation Catalysis", 《ACS NANO》 * |
| 倪永红: "《辐射技术与材料合成》", 31 July 2011, 安徽师范大学出版社 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109256568A (en) * | 2018-08-16 | 2019-01-22 | 陕西师范大学 | Monodisperse, rich Pt nanocages material of wall thickness controllable precise and the preparation method and application thereof |
| CN109256568B (en) * | 2018-08-16 | 2021-03-09 | 陕西师范大学 | Monodisperse Pt-rich nanocage material with accurately controllable wall thickness and preparation method and application thereof |
| CN111250008A (en) * | 2020-02-08 | 2020-06-09 | 浙江师范大学 | Method for synthesizing hollow sphere nano material formed by wrapping CoFe alloy in N and P co-doped carbon assembly by solvent-free thermal decomposition method |
| CN111250008B (en) * | 2020-02-08 | 2021-09-21 | 浙江师范大学 | Method for synthesizing hollow sphere nano material formed by wrapping CoFe alloy in N and P co-doped carbon assembly by solvent-free thermal decomposition method |
| CN111987328A (en) * | 2020-08-17 | 2020-11-24 | 河南师范大学 | Preparation method of electrocatalyst with nanoparticle structure for methanol fuel cell |
| CN115188978A (en) * | 2022-08-05 | 2022-10-14 | 中国科学技术大学 | Preparation method and application of supported polycrystalline surface defect high-entropy alloy catalyst |
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