CN115026298A - PdMoW ternary alloy nano material, preparation method and application in electrocatalytic oxygen reduction - Google Patents
PdMoW ternary alloy nano material, preparation method and application in electrocatalytic oxygen reduction Download PDFInfo
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- 229910002058 ternary alloy Inorganic materials 0.000 title claims abstract description 46
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 239000001301 oxygen Substances 0.000 title claims abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 14
- 230000009467 reduction Effects 0.000 title claims abstract description 13
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
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- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 9
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims abstract description 9
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 9
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 9
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000005642 Oleic acid Substances 0.000 claims abstract description 9
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000011733 molybdenum Substances 0.000 claims abstract description 9
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 9
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 7
- 239000011261 inert gas Substances 0.000 claims abstract description 7
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 claims abstract description 7
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 7
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000010937 tungsten Substances 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 239000006185 dispersion Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- FQNHWXHRAUXLFU-UHFFFAOYSA-N carbon monoxide;tungsten Chemical group [W].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] FQNHWXHRAUXLFU-UHFFFAOYSA-N 0.000 claims description 4
- GICWIDZXWJGTCI-UHFFFAOYSA-I molybdenum pentachloride Chemical compound Cl[Mo](Cl)(Cl)(Cl)Cl GICWIDZXWJGTCI-UHFFFAOYSA-I 0.000 claims description 4
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 claims description 4
- PVYPHUYXKVVURH-UHFFFAOYSA-N boron;2-methylpropan-2-amine Chemical compound [B].CC(C)(C)N PVYPHUYXKVVURH-UHFFFAOYSA-N 0.000 claims description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 12
- 239000003054 catalyst Substances 0.000 abstract description 10
- 229910052751 metal Inorganic materials 0.000 abstract description 10
- 239000002184 metal Substances 0.000 abstract description 10
- 239000002135 nanosheet Substances 0.000 abstract description 9
- 150000003839 salts Chemical class 0.000 abstract description 7
- 239000010411 electrocatalyst Substances 0.000 abstract description 5
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- 230000007774 longterm Effects 0.000 abstract description 2
- 238000005580 one pot reaction Methods 0.000 abstract description 2
- 229910001325 element alloy Inorganic materials 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 description 12
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 238000003917 TEM image Methods 0.000 description 6
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- 239000003792 electrolyte Substances 0.000 description 4
- 238000013507 mapping Methods 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910002056 binary alloy Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
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- 238000009210 therapy by ultrasound Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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- 230000004913 activation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000970 chrono-amperometry Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a PdMoW ternary alloy nano material, a preparation method and application thereof in electrocatalytic oxygen reduction. The nanometer material is prepared by adding palladium acetylacetonate, a molybdenum source and a tungsten source into a mixed solution consisting of 1-octadecene, oleylamine and oleic acid, performing ultrasonic dispersion, adding a reducing agent, introducing inert gas, and reacting to obtain the PdMoW ternary alloy nanometer material. The metal salt is prepared by a simple one-pot hydrothermal method, the importance of the metal salt on the morphology is explored by changing the type of the metal salt by a controlled variable method, and the metal salt is used as a high-efficiency electrocatalyst and shows excellent electrocatalytic performance and long-term stability. The two-dimensional nanosheet is synthesized by thermal reduction in an inert atmosphere, and the process method is simple, strong in repeatability and short in period; meanwhile, the Pd multi-element alloy catalyst is enriched by the design of the material, and a feasible idea is provided for the design of a high-efficiency catalyst for renewable energy conversion.
Description
Technical Field
The invention relates to an electro-catalytic material, a preparation method and application thereof, in particular to a PdMoW ternary alloy nano material, a preparation method and application thereof in electro-catalytic oxygen reduction.
Background
The fuel cell and the metal air cell have the advantages of high energy density, high energy conversion efficiency, low carbon emission and the like, and are considered to have good prospects in the application of the automobile field. The difficulties that should be overcome urgently to realize the wide-range application of the energy conversion device for converting chemical energy stored in fuel into electric energy through electrochemical reaction are the electrochemical reaction rate and efficiency of the two poles of the battery. Although conventional Pt has excellent electrocatalytic properties and can improve electrocatalytic efficiency, researchers are dedicated to developing new electrocatalysts due to their high cost and poor stability.
Two-dimensional nanomaterials exhibit better electrocatalytic Oxygen Reduction Reaction (ORR) performance due to the high density of exposed active centers and high surface to volume ratio. Many Pd-based binary alloy nanostructures show better performance of electrocatalytic Oxygen Reduction Reaction (ORR), and the core is that the introduced second metal can effectively regulate and control the electronic structure of Pd, and change the d-band central position of Pd, thereby facilitating the adsorption and activation of target substrate molecules, and balancing the adsorption and desorption processes of reaction intermediates or products. If a third metal element can be continuously introduced on the basis of the Pd-based binary alloy to obtain a new Pd-based ternary alloy nano structure, the electronic structure and the d-band center position of Pd can be further optimized, the electro-catalytic performance of the Pd is hopefully and greatly enhanced, and the novel Pd-based ternary alloy nano structure has great development potential.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a PdMoW ternary alloy nano material with better initial potential and polar current limiting density.
The invention also aims to provide a preparation method of the PdMoW ternary alloy nano material with better initial potential and polar current limiting density and application of the PdMoW ternary alloy nano material in electrocatalytic oxygen reduction.
The technical scheme is as follows: the preparation method of the PdMoW ternary alloy nano material comprises the following steps:
s1, ultrasonically mixing 1-octadecene, oleylamine and oleic acid to obtain a uniform mixed solution;
s2, adding palladium acetylacetonate, a molybdenum source and a tungsten source into the mixed solution obtained in the step S1, and continuing to perform ultrasonic dispersion uniformly;
s3, adding a reducing agent borane-tert-butylamine complex (BTBC) to the uniform dispersion obtained in the step S2;
and S4, rapidly introducing inert gas into the reaction system in the step S3, heating for reaction, naturally cooling to room temperature, centrifuging, washing, and drying in vacuum to obtain the PdMoW ternary alloy.
Preferably, the dosage of the 1-octadecene, oleylamine and oleic acid in the step S1 is 10 ml, 3 ml and 2 ml respectively.
Preferably, the molybdenum source in step S2 is molybdenum hexacarbonyl or molybdenum pentachloride.
Preferably, the tungsten source in step S2 is tungsten hexacarbonyl or tungsten hexachloride.
Preferably, the PdMoW ternary alloy nano material is in a nano sheet structure or a nano granular structure.
A preparation method of a preferable nanosheet PdMoW ternary alloy comprises the following steps:
s1, ultrasonically mixing 10 ml of 1-octadecene, 3 ml of oleylamine and 2 ml of oleic acid to obtain a uniform mixed solution;
s2, adding palladium acetylacetonate, molybdenum hexacarbonyl and tungsten hexacarbonyl into the mixed solution obtained in the step S1 according to a molar ratio of 1: 1: 1, continuously performing ultrasonic dispersion to be uniform;
s3, adding 100 mg of reducing agent BTBC into the uniform dispersion liquid obtained in the step S2;
and S4, quickly introducing inert gas into the reaction system in the step S3, heating to 240 ℃, reacting for 30 min, naturally cooling to room temperature, centrifuging, washing, and drying in vacuum to obtain the nanosheet PdMoW ternary alloy.
The preparation method of another preferable nano-particle PdMoW ternary alloy comprises the following steps:
s1, ultrasonically mixing 10 ml of 1-octadecene, 3 ml of oleylamine and 2 ml of oleic acid into a uniform mixed solution;
s2, adding palladium acetylacetonate, molybdenum pentachloride and tungsten hexachloride into the mixed solution obtained in the step S1 according to a molar ratio of 1: 1: 1, continuously performing ultrasonic dispersion to be uniform;
s3, adding 100 mg of reducing agent BTBC into the uniform dispersion liquid obtained in the step S2;
and S4, quickly introducing inert gas into the reaction system in the step S3, heating to 240 ℃, reacting for 30 min, naturally cooling to room temperature, centrifuging, washing, and drying in vacuum to obtain the granular PdMoW ternary alloy.
The PdMoW ternary alloy nano material is used as an electrocatalyst for reactions in electrocatalytic oxygen reduction.
The PdMoW ternary alloy nano material is used for resisting methanol.
Has the beneficial effects that: compared with the prior art, the invention has the following advantages:
(1) the PdMoW ternary alloy is prepared by adopting a thermal reduction method, wherein the combination of 1-octadecene, oleylamine and oleic acid can effectively ensure the flaky uniformity and dispersibility of the prepared sample, CO generated by thermal decomposition of carbonyl salt can be adsorbed on a certain crystal face to control the generation direction to form a flaky structure, the contact area with an electrolyte can be increased, more active sites can be exposed, the performance of the PdMoW ternary alloy in an oxygen reduction reaction is optimized, the preparation method is simple, and the repeatability is good.
(2) The PdMoW ternary alloy prepared by the thermal reduction method has good electrocatalytic oxygen reduction performance, wherein the flaky PdMoW ternary alloy obtained by using the carbonyl salt has better initial potential and extreme current limiting density, and the activity of the flaky PdMoW ternary alloy can be compared with that of commercial Pt/C.
(3) The addition of the Mo source and the W source in the invention is beneficial to reducing the cost and further reducing the application cost of the alkaline fuel cell.
(4) The morphology can be regulated and controlled by changing the type of the metal salt, and the obtained PdMoW alloy shows different electrocatalytic oxygen reduction performances.
(5) The invention simultaneously carries out methanol resistance test and cycle stability test to show that the invention has good methanol resistance and long-term stability.
Drawings
FIG. 1 is a schematic diagram of a preparation method of the flaky PdMoW ternary alloy;
FIG. 2 is an XRD (X-ray diffraction) pattern of the flaky PdMoW ternary alloy in the invention;
FIG. 3 is a TEM and HRTEM image of the lamellar PdMoW ternary alloy of the present invention, wherein A) is a TEM image at 100 nm, B) is a TEM image at 50 nm, C) is a TEM image at 20 nm, and D) is an HRTEM image at 2 nm;
FIG. 4 is a HAADF-STEM and element Mapping diagram of the sheet PdMoW ternary alloy of the present invention, wherein A) is the HAADF-STEM diagram, and B) is the element Mapping diagram;
FIG. 5 is an XRD contrast of the granular PdMoW ternary alloy and the granular PdMoW ternary alloy in the present invention;
FIG. 6 is a TEM of a particulate PdMoW according to the present invention;
FIG. 7 is a graph of ORR performance of the sheet PdMoW of the present invention, wherein a) the LSV curve obtained at 2500 rmp/min, b) the LSV curve obtained at 1600 rmp/min, c) the LSV curve obtained at 1200 rmp/min, d) the LSV curve obtained at 800 rmp/min, e) the LSV curve obtained at 400 rmp/min;
FIG. 8 is a graph comparing ORR performance of the pellet PdMoW and pellet PdMoW of the present invention, wherein a) LSV curve of the pellet PdMoW, b) LSV curve of the pellet PdMoW;
FIG. 9A) is a graph of a cycle stability test of the sheet PdMoW of the present invention; B) the methanol resistance test graphs of the flaky PdMoW and Pt/C.
Detailed Description
Example 1
Preparation of nano-sheet structure PdMoW ternary alloy (PdMoW NSs)
S1, ultrasonically mixing 10 ml of 1-octadecene, 3 ml of oleylamine and 2 ml of oleic acid into a uniform mixed solution;
s2, adding palladium acetylacetonate, molybdenum hexacarbonyl and tungsten hexacarbonyl into the mixed solution obtained in the step S1 according to a molar ratio of 1: 1: 1, continuously performing ultrasonic dispersion to be uniform;
s3, adding 100 mg of reducing agent BTBC into the uniform dispersion liquid obtained in the step S2;
and S4, quickly introducing inert gas into the reaction system in the step S3, heating to 240 ℃, reacting for 30 min, naturally cooling to room temperature, centrifuging, washing, and drying in vacuum to obtain the nanosheet PdMoW ternary alloy.
The PdMoW NSs were subjected to compositional analysis using XRD. Distinct crystalline diffraction peaks can be seen in the XRD pattern of PdMoW NSs (FIG. 2), corresponding to standard cards of cubic phase structure Pd (JCPDS-87-645), Mo (JCPDS-88-2331) and W (JCPDS-88-2339). This shows that the single nature of the phase structure successfully prepares the Pd, Mo, W trimetal alloy with high crystallinity.
The morphology and microstructure of the catalyst were characterized by TEM and HR-TEM, and its morphology was observed from TEM images at different magnifications (FIGS. 3A-C), and the PdMoW sample was obtained as a sheet structure. The good crystallinity of the prepared catalyst is again illustrated by the clear lattice fringes observed in the HR-TEM image (as in fig. 3D), wherein the lattice spacing of 0.23 nm size corresponds to the (111) crystal planes, indicating that the sample mainly exposes the (111) crystal planes, consistent with the XRD characterization results. HAADF-STEM and element Mapping graphs (FIGS. 4A-B) can see that the three elements of Pd, Mo and W are uniformly distributed on the nanosheets, which is also a condition required for proving the alloy.
Example 2
Preparation of PdMoW ternary alloy (PdMoW NPs) with nano-particle structure
S1, ultrasonically mixing 10 ml of 1-octadecene, 3 ml of oleylamine and 2 ml of oleic acid into a uniform mixed solution;
s2, adding palladium acetylacetonate, molybdenum pentachloride and tungsten hexachloride into the mixed solution obtained in the step S1 according to a molar ratio of 1: 1: 1, continuously performing ultrasonic dispersion to be uniform;
s3, adding 100 mg of reducing agent BTBC into the uniform dispersion liquid obtained in the step S2;
and S4, quickly introducing inert gas into the reaction system in the step S3, heating to 240 ℃, reacting for 30 min, naturally cooling to room temperature, centrifuging, washing, and drying in vacuum to obtain the granular PdMoW ternary alloy.
A comparison XRD pattern (figure 5) of PdMoW NPs and PdMoW for the synthesized catalysts shows similar crystallinity to PdMoW. The PdMoW NPs are subjected to structural characterization, and a TEM image (figure 6) shows that the catalyst synthesized by using the chloride is relatively uniform nanoparticles, which indicates that the carbonyl compound has irreplaceable effect in the reaction process.
The electrocatalytic performance test process of the synthesized sample is as follows: 2 mg of the synthesized electrocatalyst was weighed into a mixed solution containing 0.75 ml of isopropyl alcohol and 0.25 ml of deionized water, the dispersion was dispersed uniformly by ultrasonic treatment, and then the suspension was obtained for one hour by ultrasonic treatment. Accurately measuring 8 mul of the solution by using a liquid transfer gun, uniformly spreading the solution on the surface of the electrode of the rotating ring disk, and dripping 8 mul of the solution after drying to obtain the electrode.
The electrochemical workstation adopted for the electrochemical performance test is a Shanghai Chenghua CHI 700E type electrochemical workstation, a three-electrode test system is adopted, a glass slide electrode is adopted as a counter electrode, an Ag/AgCl electrode is adopted as a reference electrode, and the working electrode is a prepared catalyst modified rotating ring disc electrode. The electrolyte is 0.1M KOH solution. The figures herein refer to potentials and the potentials in the description are based on a reversible hydrogen electrode. Before testing, a 0.1M KOH solution was sparged with nitrogen to saturation at 100 mV s -1 Sweep the CV down at the sweep rate of (1), then pass oxygen through the 0.1M KOH solution to saturation at 100 mV s -1 Sweep the CV at a sweep rate of 5 mV s -1 Linear polarization curves were obtained at different rotational speeds (2500 rmp, 1600 rmp, 1200 rmp, 800 rmp, 400 rmp/min).
As shown in FIGS. 7 and 8, the obtained PdMoW NSs in the PdMoW ternary alloy have the optimal electrocatalytic oxygen reduction performance, and the half-wave potential of the PdMoW NSs is 0.85VvsRHE, catalytic performance superior to PdMoW NPs close to commercial Pt/C.
From the above experimental results, the PdMoW NSs electrocatalyst prepared by one-pot hydrothermal method is introduced in this chapter. The research on the maintenance of the shapes of the nano-sheets by changing the types of the metal salts by a controlled variable method shows that the carbonyl metal salts play an important role in the maintenance of the shapes of the nano-sheets. The synthesis of single-phase PdMoW NSs is proved by XRD characterization, and a Mapping graph shows the uniform distribution of three elements. Performance test in 0.1M KOH electrolyteThe half-wave potential of the model PdMoW NSs is 0.85V (vsRHE), clearly superior to the other control samples.
Example 3
To evaluate the catalyst's cycle stability, at O 2 5000 CV cycles (as shown in FIG. 9A) in saturated 0.1M KOH electrolyte, with a slight decay in half-wave potential before and after cycling, indicate that the catalyst has good cycle stability. In addition, PdMoW was evaluated for methanol resistance (FIG. 9B) using chronoamperometry at a voltage of 0.7V (V) in 0.1M KOH electrolytevsRHE), methanol was added at 400 s, and the instantaneous current at the addition changed significantly but the current density was very fast compared to that before the addition, indicating that the catalyst has good methanol resistance.
Claims (8)
1. A preparation method of PdMoW ternary alloy nano-material is characterized by comprising the following steps: the method comprises the following steps:
s1, ultrasonically mixing 1-octadecene, oleylamine and oleic acid to obtain a uniform mixed solution;
s2, adding palladium acetylacetonate, a molybdenum source and a tungsten source into the mixed solution obtained in the step S1, and continuing to perform ultrasonic dispersion to be uniform;
s3, adding a reducing agent borane-tert-butylamine complex into the uniform dispersion liquid obtained in the step S2;
and S4, introducing inert gas into the reaction system in the step S3, heating and reacting, naturally cooling to room temperature, centrifuging, washing, and drying in vacuum to obtain the PdMoW ternary alloy nano material.
2. The preparation method of the PdMoW ternary alloy nanomaterial as claimed in claim 1, wherein the preparation method comprises the following steps: the molybdenum source in step S2 is molybdenum hexacarbonyl or molybdenum pentachloride.
3. The preparation method of the PdMoW ternary alloy nanomaterial as claimed in claim 1, wherein the preparation method comprises the following steps: in the step S2, the tungsten source is tungsten hexacarbonyl or tungsten hexachloride.
4. The preparation method of the PdMoW ternary alloy nanomaterial as claimed in claim 1, wherein the preparation method comprises the following steps: the PdMoW ternary alloy nano material is in a nano flaky structure.
5. The preparation method of the PdMoW ternary alloy nanomaterial as claimed in claim 1, wherein the preparation method comprises the following steps: the PdMoW ternary alloy nano material is in a nano granular structure.
6. The PdMoW ternary alloy nano-material prepared by the preparation method of any one of claims 1 to 5.
7. The PdMoW ternary alloy nano-material prepared by the preparation method of any one of claims 1 to 5 is applied to electrocatalytic oxygen reduction.
8. The use of the PdMoW ternary alloy nanomaterial prepared by the preparation method of any one of claims 1-5 in methanol resistance.
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