CN110061246A - The preparation method of core-shell structure Te@metal electro-oxidizing-catalyzing agent - Google Patents
The preparation method of core-shell structure Te@metal electro-oxidizing-catalyzing agent Download PDFInfo
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- CN110061246A CN110061246A CN201910311598.9A CN201910311598A CN110061246A CN 110061246 A CN110061246 A CN 110061246A CN 201910311598 A CN201910311598 A CN 201910311598A CN 110061246 A CN110061246 A CN 110061246A
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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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- 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
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
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- 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
- H01M4/921—Alloys or mixtures with metallic elements
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- 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
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
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- 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 kind of preparation methods of core-shell structure Te@metal electro-oxidizing-catalyzing agent.Using hard template Te as core using precious metals pt, Pd or its alloy as shell, and polyvinylpyrrolidone is added in the method, and the Te@metal electro-oxidizing-catalyzing agent with core-shell structure is made using oil bath heating mode.Bullion content is lower in Te@metal electro-oxidizing-catalyzing agent of the invention, with excellent oxidation of alcohols performance, mass activity in liquid fuel within galvanic anode oxidation reaction can be used as efficient elctro-catalyst application liquid fuel within field of batteries far more than business Pt base catalyst.
Description
Technical field
The present invention relates to a kind of preparation methods of core-shell structure Te@metal electro-oxidizing-catalyzing agent, belong to electrochemical techniques neck
Domain.
Background technique
Chemical energy can be converted into the power generator of electric energy as one kind by fuel cell, with its potential high efficiency,
Many advantages, such as design is simple, inner fuel is directly converted obtains the extensive concern of fuel cell studies personnel.Currently, PtRu is urged
Agent is acknowledged as most promising fuel liquid battery anode catalyst, and the mistake of methanol oxidation can be effectively reduced in the addition of Ru
Current potential, and the CO poisoning capability of Pt can be greatly promoted, but nature difference existing for Pt and Ru itself, such as reduction potential phase
The problems such as difference is larger, and lattice mismatches, so that the PtRu alloy of preparation high dispersive is relatively difficult.
Chinese patent application CN103537280A discloses a kind of Pd@Pt core-shell catalyst for methanol oxidation, should
Although catalyst shows excellent electrocatalysis characteristic and durability, but in material preparation process platinum and palladium cost mistake
Height cannot achieve large-scale application.Therefore the usage amount for reducing Pt and the utilization rate for improving Pt, which become, prepares effective catalyst
Key, while cannot be to reduce the performance of fuel cell as cost.Document 1 using Te as hard template, using a large amount of Pt (Te:
Pt atomic ratio is up to 1:10), although there is more considerable electroxidation performance, there is no obtain for the performance of single Pt active site
It is utilized to maximized, preparation cost is high and does not meet theory (the ACS Appl.Mater.Interfaces of large-scale production
2016,8,16147-16153).High-content Pt is also faced in the synthesis process using base metal Cu doping PtTe nanotube, is closed
At the period it is long the problems such as, and Pt and PtTe are obtained in the structure of matter2Mixing species, be unfavorable for inspiring the best alcohol of Pt
Class electroxidation performance (770 (2019) 76-81 of Journal of Alloys and Compounds).
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of core-shell structure Te@metal electro-oxidizing-catalyzing agent.This method
Hud typed elctro-catalyst is formed using fine and close noble metal or alloy-layer cladding non-noble metallic materials, it is only necessary to few noble metal
The performance that can obtain beyond tradition Pt/Pd and Pt catalyst is combined with non-noble metallic materials.
For achieving the above object, The technical solution adopted by the invention is as follows:
The preparation method of core-shell structure Te@metal electro-oxidizing-catalyzing agent, the specific steps are as follows:
It is 4~16:1:50~300 by the mass ratio of Te, noble metal and polyvinylpyrrolidone (K29-32), by Te nanometers
Stick, precious metal salt and polyvinylpyrrolidone are added sequentially in ethylene glycol, and stirring is to being uniformly mixed, using oil bath heating side
Formula, reaction temperature are 150~180 DEG C, and soaking time is that 3~6h is cooled to room temperature after reaction, wash, are dried in vacuo
To core-shell structure Te@metal catalyst.
In the present invention, the noble metal is selected from one or both of Pt and Pd.
In the present invention, the precious metal salt is selected from H2PtCl6And PdCl2One or both of.
Preferably, the mass ratio of Te, noble metal and polyvinylpyrrolidone (K29-32) are 8:1:50.
Preferably, the reaction temperature is 150 DEG C, soaking time 3h.
Compared with prior art, the invention has the following advantages that
(1) it uses nonmetallic Te for hard template, various length is generated by the dosage of regulation surfactant and reducing agent
The nanostructure (line, stick, piece etc.) of wide ratio, then noble metal nano particles form compacted zone under the action of reducing agent, uniformly
It is supported on the surface of Te, exposes more active sites, effectively improves the utilization rate of noble metal；
(2) structure and morphology of Te@metal catalyst prepared by the present invention is core-shell structure, and noble metal active site is in
Catalyst surface, can be preferably with electrolyte contacts, and interaction between noble metal and Te makes electricity in charge and discharge process
Sub- transmission rate improves, and greatly improves the catalytic activity of Te@metal catalyst, has a better methanol oxidation susceptibility, Te, expensive
The mass ratio of metal and polyvinylpyrrolidone (K29-32) are 8:1:50, the best performance of material, and mass activity can achieve
2.5A/mg-1, excellent anodic oxidation performance allows to be widely used in fuel liquid battery.
Detailed description of the invention
Fig. 1 is the XRD diagram of Te nanometer rods made from embodiment 1.
Fig. 2 is the TEM figure of Te nanometer rods made from embodiment 1.
Fig. 3 is the XRD diagram of -150 DEG C of -3h electro-oxidizing-catalyzing agent of core-shell structure Te@Pt (8:1:50) made from embodiment 1.
Fig. 4 is the TEM figure of -150 DEG C of -3h electro-oxidizing-catalyzing agent of core-shell structure Te@Pt (8:1:50) made from embodiment 1.
Fig. 5 is that the line of -150 DEG C of -3h electro-oxidizing-catalyzing agent of core-shell structure Te@Pt (8:1:50) made from embodiment 1 sweeps member
Plain distribution map.
Fig. 6 be -150 DEG C of -3h electro-oxidizing-catalyzing agent of core-shell structure Te@Pt (8:1:50) made from embodiment 1 in 1MKOH and
1MCH3Catalytic performance curve graph in OH electrolyte.
Fig. 7 is the XRD diagram of -150 DEG C of -3h electro-oxidizing-catalyzing agent of core-shell structure Te@Pt (8:1:300) made from embodiment 2.
Fig. 8 is the TEM figure of -150 DEG C of -3h electro-oxidizing-catalyzing agent of core-shell structure Te@Pt (8:1:300) made from embodiment 2.
Fig. 9 is -150 DEG C of -3h electro-oxidizing-catalyzing agent of core-shell structure Te@Pt (8:1:300) made from embodiment 2 in 1MKOH
And 1MCH3Catalytic performance curve graph in OH electrolyte.
Figure 10 is the XRD diagram of -150 DEG C of -6h electro-oxidizing-catalyzing agent of core-shell structure Te@Pt (8:1:50) made from embodiment 3.
Figure 11 is the TEM figure of -150 DEG C of -6h electro-oxidizing-catalyzing agent of core-shell structure Te@Pt (8:1:50) made from embodiment 3.
Figure 12 is -150 DEG C of -6h electro-oxidizing-catalyzing agent of core-shell structure Te@Pt (8:1:50) made from embodiment 3 in 1MKOH
And 1MCH3Catalytic performance curve graph in OH electrolyte.
Figure 13 is the XRD diagram of -180 DEG C of -3h electro-oxidizing-catalyzing agent of core-shell structure Te@Pt (8:1:50) made from embodiment 4.
Figure 14 is the TEM figure of -180 DEG C of -3h electro-oxidizing-catalyzing agent of core-shell structure Te@Pt (8:1:50) made from embodiment 4.
Figure 15 is -180 DEG C of -3h electro-oxidizing-catalyzing agent of core-shell structure Te@Pt (8:1:50) made from embodiment 4 in 1MKOH
And 1MCH3Catalytic performance curve graph in OH electrolyte.
Figure 16 is the XRD diagram of -150 DEG C of -3h electro-oxidizing-catalyzing agent of core-shell structure Te@Pt (4:1:50) made from embodiment 5.
Figure 17 is the TEM figure of -150 DEG C of -3h electro-oxidizing-catalyzing agent of core-shell structure Te@Pt (4:1:50) made from embodiment 5.
Figure 18 is -150 DEG C of -3h electro-oxidizing-catalyzing agent of core-shell structure Te@Pt (4:1:50) made from embodiment 5 in 1MKOH
And 1MCH3Catalytic performance curve graph in OH electrolyte.
Figure 19 is the XRD of -150 DEG C of -3h electro-oxidizing-catalyzing agent of core-shell structure Te@Pt (16:1:50) made from embodiment 6
Figure.
Figure 20 is the TEM of -150 DEG C of -3h electro-oxidizing-catalyzing agent of core-shell structure Te@Pt (16:1:50) made from embodiment 6
Figure.
Figure 21 is -150 DEG C of -3h electro-oxidizing-catalyzing agent of core-shell structure Te@Pt (16:1:50) made from embodiment 6 in 1MKOH
And 1MCH3Performance chart in OH electrolyte.
Figure 22 is the XRD diagram of core-shell structure Te@Pd electro-oxidizing-catalyzing agent made from embodiment 7.
Figure 23 is the TEM figure of core-shell structure Te@Pd electro-oxidizing-catalyzing agent made from embodiment 7.
Figure 24 is core-shell structure Te@Pd electro-oxidizing-catalyzing agent made from embodiment 7 in 0.5MH2SO4It is electrolysed with 0.5MHCOOH
Catalytic performance curve graph in liquid.
Figure 25 is the XRD diagram of core-shell structure Te@PtPd electro-oxidizing-catalyzing agent made from embodiment 8.
Figure 26 is the TEM figure of core-shell structure Te@PtPd electro-oxidizing-catalyzing agent made from embodiment 8.
Figure 27 is that the line of core-shell structure Te@PtPd electro-oxidizing-catalyzing agent made from embodiment 8 sweeps distribution diagram of element.
Figure 28 is core-shell structure Te@PtPd electro-oxidizing-catalyzing agent made from embodiment 8 in 1MKOH and 1MCH3OH electrolyte
In catalytic performance curve graph.
Figure 29 is the XRD diagram of electro-oxidizing-catalyzing agent made from comparative example 1.
Figure 30 is the TEM figure of electro-oxidizing-catalyzing agent made from comparative example 1.
Figure 31 is the XRD diagram of electro-oxidizing-catalyzing agent made from comparative example 2.
Figure 32 is the TEM figure of electro-oxidizing-catalyzing agent made from comparative example 2.
Figure 33 is the XRD diagram of electro-oxidizing-catalyzing agent made from comparative example 3.
Figure 34 is the TEM figure of electro-oxidizing-catalyzing agent made from comparative example 3.
Figure 35 is the XRD diagram of electro-oxidizing-catalyzing agent made from comparative example 4.
Figure 36 is the TEM figure of electro-oxidizing-catalyzing agent made from comparative example 4.
Specific embodiment
Below with reference to embodiment and attached drawing, the invention will be further described.
Embodiment 1
The preparation of -150 DEG C of -3h electro-oxidizing-catalyzing agent of core-shell structure Te@Pt (8:1:50):
The first step, by 230mg sodium tellurite, 450mg ascorbic acid, 100mg polyvinylpyrrolidone is added sequentially to contain
Have in the 100mL boiling flask of 30mL ethylene glycol, stirring at normal temperature to be uniformly mixed.It is 100mL that above-mentioned solution, which is transferred to volume,
Polytetrafluoro substrate in, setting oven temperature be 150 DEG C, soaking time 6h.To the end of reacting and be cooled to room temperature, spend from
Sub- water, acetone, ethyl alcohol repeatedly wash, and filter, and vacuum drying obtains silvery white gloss substance, test through powder X-ray RD diffractometer, sample
Product are Te, and for testing in next step.
Second step, at room temperature, successively 16mgTe, 66uLH2PtCl6Solution (Pt:30mg/mL) and 100mg polyethylene pyrrole
Pyrrolidone is added in the 250mL boiling flask containing 100mL ethylene glycol, is stirred to uniformly mixed.Using oil bath heating mode,
150 DEG C are set by reaction temperature, soaking time 3h.Be cooled to room temperature, it is washed be dried to obtain core-shell structure Te@Pt (8:
1:50) -150 DEG C of -3h electro-oxidizing-catalyzing agent.
Fig. 1 be embodiment 1 made from Te nanometer rods XRD diagram, as can be seen from the figure the characteristic peak of Te clearly, position
It sets completely the same with standard PDF card (36-1425), shows that the crystallinity of Te is fabulous.
Fig. 2 is the TEM figure of Te nanometer rods made from embodiment 1, and as can be seen from the figure Te nanometer rods pattern is highly uniform.
Fig. 3 is the XRD diagram of -150 DEG C of -3h electro-oxidizing-catalyzing agent of core-shell structure Te@Pt (8:1:50) made from embodiment 1,
It can be seen from the figure that the principal character peak of Te still remains, but obviously die down, while three characteristic peaks of Pt occur,
(111), (200) and (220) crystal face for corresponding to Pt respectively at 39.7 °, 46.2 ° and 67.4 °, illustrates the formation of Pt, and
The feature peak intensity of Te obviously weakens.
Fig. 4 is the TEM figure of -150 DEG C of -3h electro-oxidizing-catalyzing agent of core-shell structure Te@Pt (8:1:50) that embodiment 1 obtains,
It can be seen from the figure that the pattern of Te nanometer rods after long-time oil bath processing, can still keep club shaped structure, surface distribution
One layer of fine and close Pt layer.
Fig. 5 is the linear sweep graph for -150 DEG C of -3h electro-oxidizing-catalyzing agent of core-shell structure Te@Pt (8:1:50) that embodiment 1 obtains,
It can more determine that Te nanorod surfaces form fine and close Pt layer, show the formation of core-shell structure Te@Pt electro-oxidizing-catalyzing agent.
Fig. 6 be obtained -150 DEG C of -3h electro-oxidizing-catalyzing agent of core-shell structure Te@Pt (8:1:50) of embodiment 1 in 1MKOH and
1MCH3Catalytic performance curve graph in OH electrolyte.It should be noted that the electrochemistry of sample obtained by all Te@Pt cases
Experiment carries out on Bio-Logic VSP multi-channel electrochemical work station, and using the three-electrode system of standard, working electrode is
Platinum carbon electrode is platinum electrode to electrode, and reference electrode is saturated calomel electrode, and (25 DEG C) progress, electrolyte are at normal temperature
1MKOH and 1MCH3The mixed liquor of OH, it can be seen that the methanol oxidation susceptibility of the catalyst be far superior to business PtRu/C and
Pt/C, mass activity can achieve 2.3A mg-1。
Embodiment 2
The preparation of -150 DEG C of -3h electro-oxidizing-catalyzing agent of core-shell structure Te@Pt (8:1:300): at room temperature, successively Example
Te 16mg made from 1,66uLH2PtCl6Solution (Pt:30mg/mL) and 600mg polyvinylpyrrolidone are added to containing 100mL
In the 250mL boiling flask of ethylene glycol, magnetic agitation to be uniformly mixed.Using oil bath heating mode, reaction temperature is tuned into 150
DEG C, soaking time 3h.It is cooled to room temperature, it is washed to be dried to obtain -150 DEG C of -3h electricity oxygen of core-shell structure Te@Pt (8:1:300)
Change catalyst.
Fig. 7 is the XRD diagram of -150 DEG C of -3h electro-oxidizing-catalyzing agent of core-shell structure Te@Pt (8:1:300) made from embodiment 2,
It can be seen from the figure that the principal character peak of Te still remains, also there are three characteristic peaks of Pt, at 39.7 °, 46.2 ° and 67.4 °
Place corresponds to (111), (200) and (220) crystal face of Pt respectively, illustrates the formation of Pt.
Fig. 8 is the TEM figure of -150 DEG C of -3h electro-oxidizing-catalyzing agent of core-shell structure Te@Pt (8:1:300) that embodiment 2 obtains,
It can be seen from the figure that the pattern of Te nanometer rods is after long-time oil bath processing, stick surface is dispersed with one layer of fine and close Pt layer.
Fig. 9 is obtained -150 DEG C of -3h electro-oxidizing-catalyzing agent of core-shell structure Te@Pt (8:1:300) of embodiment 2 in 1MKOH
And 1MCH3Catalytic performance curve graph in OH electrolyte.The methanol oxidation susceptibility of the catalyst is preferable, and mass activity can achieve
1.3A mg-1。
Embodiment 3
The preparation of -150 DEG C of -6h electro-oxidizing-catalyzing agent of core-shell structure Te@Pt (8:1:50): at room temperature, successively Example 1
Te16mg made from the first step, 66uLH2PtCl6Solution (Pt:30mg/mL) and 100mg polyvinylpyrrolidone be added to containing
In the 250mL boiling flask of 100mL ethylene glycol, magnetic agitation to be uniformly mixed.Using oil bath heating mode, by reaction temperature tune
At 150 DEG C, soaking time 6h.It is cooled to room temperature, it is washed to be dried to obtain -150 DEG C of -6h of core-shell structure Te@Pt (8:1:50)
Electro-oxidizing-catalyzing agent.
Figure 10 is the XRD diagram of -150 DEG C of -6h electro-oxidizing-catalyzing agent of core-shell structure Te@Pt (8:1:50) made from embodiment 3,
It can be seen from the figure that the catalyst has more apparent three Pt characteristic peaks, it is right respectively at 39.7 °, 46.2 ° and 67.4 °
(111), (200) and (260) crystal face for answering Pt, illustrates the formation of Pt.
Figure 11 is the TEM figure of -150 DEG C of -6h electro-oxidizing-catalyzing agent of core-shell structure Te@Pt (8:1:50) that embodiment 3 obtains,
It can be seen from the figure that the pattern of Te nanometer rods after long-time oil bath processing, can still keep club shaped structure, surface distribution
Pt particle formed compacted zone.
Figure 12 is obtained -150 DEG C of -6h electro-oxidizing-catalyzing agent of core-shell structure Te@Pt (8:1:50) of embodiment 3 in 1MKOH
And 1MCH3Catalytic performance curve graph in OH electrolyte.The methanol oxidation susceptibility of the catalyst is preferable, and mass activity can achieve
1.1A mg-1。
Embodiment 4
The preparation of -180 DEG C of -3h electro-oxidizing-catalyzing agent of core-shell structure Te@Pt (8:1:50): at room temperature, successively Example 1
Te16mg made from the first step, 66uLH2PtCl6Solution (Pt:30mg/mL) and 100mg polyvinylpyrrolidone be added to containing
In the 250mL boiling flask of 100mL ethylene glycol, magnetic agitation to be uniformly mixed.Using oil bath heating mode, by reaction temperature tune
At 180 DEG C, soaking time 3h.It is cooled to room temperature, it is washed to be dried to obtain -180 DEG C of -3h of core-shell structure Te@Pt (8:1:50)
Electro-oxidizing-catalyzing agent.
Figure 13 is the XRD diagram of -180 DEG C of -3h electro-oxidizing-catalyzing agent of core-shell structure Te@Pt (8:1:50) made from embodiment 4,
It can be seen from the figure that the catalyst has more apparent three Pt characteristic peaks, it is right respectively at 39.7 °, 46.2 ° and 67.4 °
(111), (200) and (220) crystal face for answering Pt, illustrates the formation of Pt, and the characteristic peak of Te is very unobvious, this is because warm
It spends caused by height.
Figure 14 is the TEM figure of -180 DEG C of -3h electro-oxidizing-catalyzing agent of core-shell structure Te@Pt (8:1:50) that embodiment 4 obtains,
It can be seen from the figure that the pattern of Te nanometer rods can still keep club shaped structure after longer time oil bath processing, formation
Pt layers are supported in an orderly manner on Te stick surface.
Figure 15 is obtained -180 DEG C of -3h electro-oxidizing-catalyzing agent of core-shell structure Te@Pt (8:1:50) of embodiment 4 in 1MKOH
And 1MCH3The methanol oxidation susceptibility of catalytic performance curve graph in OH electrolyte, the catalyst is also preferable, and mass activity can reach
To 1.4A mg-1。
Embodiment 5
The preparation of -150 DEG C of -3h electro-oxidizing-catalyzing agent of core-shell structure Te@Pt (4:1:50): at room temperature, successively Example 1
Te 8mg made from the first step, 66uLH2PtCl6Solution (Pt:30mg/mL) and 100mg polyvinylpyrrolidone be added to containing
In the 250mL boiling flask of 100mL ethylene glycol, magnetic agitation to be uniformly mixed.Using oil bath heating mode, by reaction temperature tune
At 150 DEG C, soaking time 3h.It is cooled to room temperature, it is washed to be dried to obtain -150 DEG C of -3h of core-shell structure Te@Pt (4:1:50)
Electro-oxidizing-catalyzing agent.
Figure 16 is the XRD diagram of -150 DEG C of -3h electro-oxidizing-catalyzing agent of core-shell structure Te@Pt (4:1:50) made from embodiment 5,
It can be seen from the figure that the catalyst has more apparent three Pt characteristic peaks, it is right respectively at 39.7 °, 46.2 ° and 67.4 °
(111), (200) and (220) crystal face for answering Pt, illustrates the formation of Pt.
Figure 17 is the TEM figure of -150 DEG C of -3h electro-oxidizing-catalyzing agent of core-shell structure Te@Pt (4:1:50) that embodiment 5 obtains,
It can be seen from the figure that comparatively, the reduction of Te dosage causes excessive load so that the Pt particle of surface distribution increases, but
It is still it can be seen that surface forms thicker Pt layer.
Figure 18 is obtained -150 DEG C of -3h electro-oxidizing-catalyzing agent of core-shell structure Te@Pt (4:1:50) of embodiment 5 in 1MKOH
And 1MCH3The methanol oxidation susceptibility of catalytic performance curve graph in OH electrolyte, the catalyst is also preferable, and mass activity can reach
To 0.9A mg-1。
Embodiment 6
The preparation of -150 DEG C of -3h electro-oxidizing-catalyzing agent of core-shell structure Te@Pt (16:1:50): at room temperature, successively Example
Te 32mg, 66uLH made from 1 first step2PtCl6Solution (Pt:30mg/mL) and 100mg polyvinylpyrrolidone are added to and contain
Have in the 250mL boiling flask of 100mL ethylene glycol, magnetic agitation to be uniformly mixed.Using oil bath heating mode, by reaction temperature
150 DEG C are tuned into, soaking time 3h.It is cooled to room temperature, washed suction filtration is dried to obtain core-shell structure Te@Pt (16:1:50)-
150 DEG C of -3h electro-oxidizing-catalyzing agent.
Figure 19 is the XRD of -150 DEG C of -3h electro-oxidizing-catalyzing agent of core-shell structure Te@Pt (16:1:50) made from embodiment 6
Figure, it can be seen from the figure that the apparent Te characteristic peak of the catalyst, and three Pt feature peak intensities are weaker, but at 39.7 °,
(111), (200) and (200) crystal face that Pt can be still respectively corresponded at 46.2 ° and 67.4 °, illustrates the formation of Pt, this is
Since the amount of Pt is too low, it is relatively thin caused that surface is formed by Pt.
Figure 20 is the TEM for -150 DEG C of -3h electro-oxidizing-catalyzing agent of core-shell structure Te@Pt (16:1:50) that embodiment 6 obtains
Figure, it can be seen from the figure that the pattern of Te nanometer rods after long-time oil bath processing, can still keep club shaped structure, Pt is used
The reduction of amount is so that fine and close Pt layers of surface distribution become thinner.
Figure 21 is obtained -150 DEG C of -3h electro-oxidizing-catalyzing agent of core-shell structure Te@Pt (16:1:50) of embodiment 6 in 1MKOH
And 1MCH3The methanol oxidation susceptibility of catalytic performance curve graph in OH electrolyte, the catalyst is also preferable, and mass activity can reach
To 1.3A mg-1。
Embodiment 7
The preparation of core-shell structure Te@Pd catalyst: at room temperature, successively Te16mg made from 1 first step of Example,
66uLPdCl2It is flat that solution (Pd:30mg/mL) and 100mg polyvinylpyrrolidone are added to the 250mL containing 100mL ethylene glycol
In the flask of bottom, stir to uniformly mixed.Using oil bath heating mode, 150 DEG C are set by reaction temperature, soaking time 3h.
It is cooled to room temperature, is washed with deionized and is dried to obtain core-shell structure Te@Pd electro-oxidizing-catalyzing agent.
Figure 22 is the XRD diagram of core-shell structure Te@Pd electro-oxidizing-catalyzing agent made from embodiment 7, it can be seen from the figure that should
The apparent Te characteristic peak of catalyst, and three Pd feature peak intensities are weaker, but at 40.1 °, still can be at 46.6 ° and 68.1 °
(111), (200) and (220) crystal face for respectively corresponding Pd, illustrates the formation of Pd.
Figure 23 is the TEM figure of core-shell structure Te@Pd catalyst made from embodiment 7.The pattern of Te nanometer rods is for a long time
After oil bath processing, club shaped structure can be still kept, surface is dispersed with one layer of fine and close Pd layer.
Figure 24 is core-shell structure Te@Pd electro-oxidizing-catalyzing agent made from embodiment 7 in 0.5MH2SO4It is electrolysed with 0.5MHCOOH
Catalytic performance curve graph in liquid.It should be noted that the electrochemistry experiment of sample obtained by the embodiment is in Bio-Logic
It is carried out on VSP multi-channel electrochemical work station, using the three-electrode system of standard, working electrode is platinum carbon electrode, is to electrode
Platinum electrode, reference electrode are saturated calomel electrode, at normal temperature (25 DEG C) progress, electrolyte 0.5H2SO4And 0.5MHCOOH
Mixed liquor, it can be seen that the Oxidation of Formic Acid of the catalyst is had excellent performance, and mass activity can achieve 1.6Amg-1。
Embodiment 8
At room temperature, the 16mgTe that Example 1 obtains, is successively added dropwise 66uLH2PtCl6Solution (Pt:30mg/mL),
66uLPdCl2It is flat that solution (Pd:30mg/mL) and 100mg polyvinylpyrrolidone are added to the 250mL containing 100mL ethylene glycol
In the flask of bottom, magnetic agitation to be uniformly mixed.Using oil bath heating mode, 150 DEG C are set by reaction temperature, soaking time is
3h.It is to be cooled arrive room temperature, it is washed to be dried to obtain core-shell structure Te@PtPd electro-oxidizing-catalyzing agent.
Figure 25 is the XRD diagram of core-shell structure Te@PtPd catalyst made from embodiment 8.Wherein, there is apparent Pt's
Characteristic peak and weaker Pd characteristic peak, show during oil bath, form PtPd alloy in Te nanorod surfaces.
Figure 26 is the TEM figure of core-shell structure Te@PtPd catalyst made from embodiment 8.The pattern of Te nanometer rods is when long
Between oil bath processing after, can still keep club shaped structure, surface is dispersed with one layer of fine and close PtPd alloy-layer.
Figure 27 is that the line of core-shell structure Te@PtPd catalyst made from embodiment 8 sweeps distribution diagram of element.It can more determine
The presence of Te nanorod surfaces Pt, Pd element shows the formation of core-shell structure Te@PtPd electro-oxidizing-catalyzing agent.
Figure 28 is core-shell structure Te@PtPd catalyst made from embodiment 8 in 1MKOH and 1MCH3Urging in OH electrolyte
Change performance chart, shows that core-shell structure Te@PtPd electro-oxidizing-catalyzing agent has higher first than the PtPd/C catalyst of business
Alcohol catalysis performance.
Comparative example 1
At room temperature, successively Te 4mg, 66uLH made from 1 first step of Example2PtCl6Solution (Pt:30mg/mL) and
100mg polyvinylpyrrolidone is added in the 250mL boiling flask containing 100mL ethylene glycol, is stirred to uniformly mixed.Using
Reaction temperature is tuned into 150 DEG C, soaking time 3h by oil bath heating mode.It is cooled to room temperature, it is washed to be dried to obtain electroxidation
Catalyst.
Figure 29 is the XRD diagram of electro-oxidizing-catalyzing agent made from comparative example 1.It can be seen from the figure that Pt characteristic peak is brighter
It is aobvious, and the characteristic peak of Te is almost without this is because the dosage of Te is very few when being added.
Figure 30 is the TEM figure of electro-oxidizing-catalyzing agent made from comparative example 1.It can be seen from the figure that Pt particle agglomeration compares
Obviously, and not the sharp interface between Te and Pt is seen, so core-shell structure does not obtain under such condition.
Comparative example 2
At room temperature, successively Te 16mg, 66uLH made from 1 first step of Example2PtCl6Solution (Pt:30mg/mL) and
100mg polyvinylpyrrolidone is added in the 250mL boiling flask containing 100mL ethylene glycol, is stirred to uniformly mixed.Using
Reaction temperature is tuned into 100 DEG C, soaking time 3h by oil bath heating mode.It is cooled to room temperature, it is washed to be dried to obtain electroxidation
Catalyst.
Figure 31 is the XRD diagram of electro-oxidizing-catalyzing agent made from comparative example 2.It can be seen from the figure that Te characteristic peak is brighter
The aobvious and characteristic peak of Pt is almost without this is because temperature is too low to be led to Pt there is no generate.
Figure 32 is the TEM figure of electro-oxidizing-catalyzing agent made from comparative example 2.It can be seen from the figure that almost without Pt particle
Generation, can only see smooth Te nanometer rods.
Comparative example 3
At room temperature, successively Te 16mg, 66uLH made from 1 first step of Example2PtCl6Solution (Pt:30mg/mL) adds
Enter into the 250mL boiling flask containing 100mL ethylene glycol, stirs to uniformly mixed.Using oil bath heating mode, by reaction temperature
Degree is tuned into 150 DEG C, soaking time 3h.It is cooled to room temperature, it is washed to be dried to obtain electro-oxidizing-catalyzing agent.
Figure 33 is the XRD diagram of electro-oxidizing-catalyzing agent made from comparative example 3.It can be seen from the figure that Te characteristic peak is brighter
Aobvious, the characteristic peak of Pt is weaker.
Figure 34 is the TEM figure of electro-oxidizing-catalyzing agent made from comparative example 3.It can be seen from the figure that there is larger Pt particle
It generates, due to there is no addition polyvinylpyrrolidone, so without apparent core-shell structure.
Comparative example 4
At room temperature, successively Te 16mg, 66uLH made from 1 first step of Example2PtCl6Solution (Pt:30mg/mL) and
100mg polyvinylpyrrolidone is added in the 250mL boiling flask containing 100mL ethylene glycol, magnetic agitation to be uniformly mixed.
Using oil bath heating mode, reaction temperature is tuned into 150 DEG C, soaking time 9h.It is cooled to room temperature, it is washed to be dried to obtain electricity
Oxidation catalyst.
Figure 35 is the XRD diagram of electro-oxidizing-catalyzing agent made from comparative example 4.It can be seen from the figure that Te characteristic peak is brighter
Aobvious, the characteristic peak of Pt is also obvious, shows the formation of Pt.
Figure 36 is the TEM figure of electro-oxidizing-catalyzing agent made from comparative example 4.It can be seen from the figure that too long soaking time,
So that Te stick shows some defects, also without apparent core-shell structure.
Claims (7)
1. the preparation method of core-shell structure Te@metal electro-oxidizing-catalyzing agent, which is characterized in that specific step is as follows:
By Te, noble metal and polyvinylpyrrolidone (K29-32) mass ratio be 4~16:1:50~300, by Te nanometer rods,
Precious metal salt and polyvinylpyrrolidone are added sequentially in ethylene glycol, and stirring is to being uniformly mixed, using oil bath heating mode, instead
Answering temperature is 150~180 DEG C, and soaking time is that 3~6h is cooled to room temperature after reaction, is washed, vacuum drying obtains core
Shell structure Te@metal catalyst.
2. preparation method according to claim 1, which is characterized in that the noble metal be selected from one of Pt and Pd or
Two kinds.
3. preparation method according to claim 1, which is characterized in that the precious metal salt is selected from H2PtCl6And PdCl2
One or both of.
4. preparation method according to claim 1, which is characterized in that Te, noble metal and the polyvinylpyrrolidone
(K29-32) mass ratio is 8:1:50.
5. preparation method according to claim 1, which is characterized in that the reaction temperature is 150 DEG C, and soaking time is
3h。
6. core-shell structure Te@metal electro-oxidizing-catalyzing agent made from preparation method according to any one of claims 1 to 5.
7. the application in core-shell structure Te@metal electro-oxidizing-catalyzing agent liquid fuel within battery according to claim 6.
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| CN113058660A (en) * | 2021-03-31 | 2021-07-02 | 扬州大学 | Catalyst carrier and preparation method thereof, catalyst and preparation method and application thereof |
| CN114657598A (en) * | 2022-03-21 | 2022-06-24 | 深圳信息职业技术学院 | Core-shell structure catalyst and preparation method and application thereof |
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| CN114657598A (en) * | 2022-03-21 | 2022-06-24 | 深圳信息职业技术学院 | Core-shell structure catalyst and preparation method and application thereof |
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