CN109449450A - A kind of palladium ruthenium nanometer thorn assembling body catalyst and preparation method thereof - Google Patents
A kind of palladium ruthenium nanometer thorn assembling body catalyst and preparation method thereof Download PDFInfo
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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
- H01M4/9041—Metals or alloys
- H01M4/905—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC
- H01M4/9058—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC of noble metals or noble-metal based alloys
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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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
- H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
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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
A kind of palladium ruthenium nanometer thorn assembling body catalyst and preparation method thereof, matches chlorine palladium acid sodium and chlorination ruthenium solution of the concentration between 1~30mM, hydrochloric acid solution and concentration ascorbic acid solution 0.01~0.5M between of the concentration between 1~10M respectively；The chlorine palladium acid sodium and the mixing of chlorination ruthenium solution that total volume is 3.0mL are taken respectively, and the hydrochloric acid solution that 0.1~0.5mL has been prepared then is added, adds the potassium bromide and F127 between 0.1~0.5g, is uniformly mixed；Finally add the ascorbic acid solution of 1~10mL；It after solution is sufficiently mixed, is placed in oil bath pan and is heated between 70~130 DEG C, after reaction 0.1~3 hour, washing, centrifugation, drying obtain the palladium ruthenium nanometer thorn assembling body catalyst.Preparation process of the present invention is simple, and the reaction time is short, and at normal temperatures and pressures, material obtained has excellent electrochemistry Oxidation of Formic Acid performance.
Description
(1) technical field
The present invention relates to a kind of palladium ruthenium nanometers to pierce assembling body catalyst and preparation method thereof, which can be used for electro-catalysis
The research of Oxidation of Formic Acid reaction.
(2) background technique
Direct methanoic acid fuel cell is considered a kind of up-and-coming in terms of room temperature power generation and portable electronic device
The energy.The catalytic performance of Oxidation of Formic Acid significantly determines the performance of direct methanoic acid fuel cell, therefore is applied to formic acid
The catalyst of oxidation has had received widespread attention and has studied.Studies have shown that palladium catalyst is due to direct reaction path
(HCOOH→CO2+2H++2e-) presence, catalytic activity with higher is reacted to Oxidation of Formic Acid under the conditions of low overpotential.This
Outside, palladium catalyst has good CO tolerance catalysts ability, this is conducive to the durability for improving Oxidation of Formic Acid reaction.But palladium
Reserves are low and expensive, hinder large-scale commercial applications application of the palladium catalyst in direct methanoic acid fuel cell.Therefore, it reduces
The content of noble metal in the catalyst is very important actual application.
It is generally known that palladium and other metallic alloying can not only reduce the content of noble metal in the catalyst, Er Qieke
To improve its catalytic activity in Oxidation of Formic Acid reaction.The lattice that the combination of palladium atom and other atoms will lead to palladium atom is answered
Become and have adjusted the electronic structure of palladium atom, to form more active sites, and then improves the catalytic activity of palladium catalyst.
For example, Yang Jun etc. proposes the myriapod copper palldium alloy nanometer for preparing morphology controllable by electrochemical displacement reaction in oleyl amine
Crystal, the intervention of copper atom can lead to the contraction of palladium lattice, weaken the bond strength of reaction intermediate Yu palladium surface, from
And catalyst is improved for catalytic performance (Chen, the D. of Oxidation of Formic Acid；Sun,P.；Liu,H.； Yang,J.Bimetallic
Cu–Pd alloy multipods and their highly electrocatalytic performance for
formic acid oxidation and oxygen reduction.J.Mater.Chem. A,2017,5,4421-4429)。
This alloy strategy enlightens us will improve its Oxidation of Formic Acid catalytic by controlling pattern and the composition of palladium-based catalyst
Energy.
Branch shape nanostructure is due to unique electro-catalysis structural advantage, the extensive concern caused.In branch
Nanostructure in, the porous structure of connection can effectively promote the diffusion of ion and the infiltration of electrolyte, and anti-for catalysis
The active site of enough exposures should be provided.It, in this way can be with moreover, self-supporting nanometer multi-branched is not easy to assemble catalyst
It is effectively prevented from the reduction of active site in catalytic process.Although achieving progress in terms of metal alloy, high branch is manufactured
Changing metal alloy is still a huge challenge.In general, the not inherent driving force in the structural metal face-centered cubic (fcc)
Promote to spontaneously form anisotropy nanostructure in aqueous solution, therefore, the preparation of branch's metal Nano structure generallys use
Multistep synthetic strategy (for example, seed mediated growth method, selective etch method, redox displacement method etc.).These multi-step synthesis sides
Method is difficult to carry out prepare with scale due to its complicated and time-consuming process.Therefore, one kind directly synthesis highly -branched metal is developed to urge
The method of agent has become the hot spot of research.
(3) summary of the invention
It is an object of the present invention to provide the preparation methods that a kind of palladium ruthenium nanometer pierces assembling body catalyst, and to catalytic electrochemical
The research of Oxidation of Formic Acid reaction.
The technical solution adopted by the present invention is that:
A kind of palladium ruthenium nanometer thorn assembling body catalyst, prepares by the following method:
(1) match chlorine palladium acid sodium and chlorination ruthenium solution of the concentration between 1~30mM respectively, concentration is between 1~10M
The ascorbic acid solution of hydrochloric acid solution and concentration between 0.01~0.5M；
(2) the chlorine palladium acid sodium and the mixing of chlorination ruthenium solution that total volume is 3.0mL are taken respectively, and 0.1~0.5mL is then added
The hydrochloric acid solution prepared adds potassium bromide and F127 between 0.01~0.5g, is uniformly mixed；Finally add 1~
The ascorbic acid solution of 10mL, ultrasonic mixing 5~30 minutes；
(3) it after solution is sufficiently mixed, is placed in oil bath pan and is heated between 70~130 DEG C, after reaction 0.1~3 hour,
Washing, centrifugation, drying obtain the palladium ruthenium nanometer thorn assembling body catalyst.
The selection of reaction condition has great influence to the structure for preparing palladium ruthenium catalyst, be added in reaction potassium bromide be by
In Br-It can be adsorbed on (100) crystal face of Face-centred Cubic Metals, can selectively prevent the growth of metal on (100) crystal face, have
Conducive to the growth of dendrite.Ru3+Have the function of shape directed agents, may eventually lead to the formation of dendritic nanocrystal.In addition, choosing
Triblock copolymer F127 is selected as end-capping reagent, the dispersibility that can effectively improve nuclearing centre reduces the possibility reunited, therefore
Lead to the formation of the dispersed thorn assembly of three-dimensional manometer well.During the preparation process, changing ratio that presoma is added can be with
Control the pattern and structure of palladium ruthenium.
A kind of preparation method of palladium ruthenium nanometer thorn assembling body catalyst, described method includes following steps: (1) matching respectively
Chlorine palladium acid sodium and chlorination ruthenium solution of the concentration between 1~30mM, hydrochloric acid solution and concentration of the concentration between 1~10M exist
Ascorbic acid solution between 0.01~0.5M；
(2) the chlorine palladium acid sodium and the mixing of chlorination ruthenium solution that total volume is 3.0mL are taken respectively, and 0.1~0.5mL is then added
The hydrochloric acid solution prepared adds potassium bromide and F127 between 0.01~0.5g, is uniformly mixed；Finally add 1~
The ascorbic acid solution of 10mL, ultrasonic mixing 5~30 minutes；
(3) it after solution is sufficiently mixed, is placed in oil bath pan and is heated between 70~130 DEG C, after reaction 0.1~3 hour,
Washing, centrifugation, drying obtain the palladium ruthenium nanometer thorn assembling body catalyst.
Further, the concentration and volume of control chlorine palladium acid sodium, ruthenic chloride and ascorbic acid, the amount of potassium bromide and F127, with
And the temperature and time of reaction controls the pattern and structure of palladium ruthenium.
The reaction of electrochemical catalysis Oxidation of Formic Acid, specific performance test operating procedure are carried out at normal temperatures and pressures are as follows:
(1) sample dispersion of 1~10mg is weighed in ultrapure water, and ultrasound obtains uniform dispersion liquid in 30 minutes, takes 1~10
The Nafion solution (0.5wt%) that μ L drop drips 1~10 μ L after glassy carbon electrode surface, 50 DEG C of dryings is covered on catalyst surface,
Working electrode is made.Platinum electrode is used as to electrode simultaneously, and Ag/AgCl electrode is carried out as reference electrode composition three-electrode system
Redox test；
(2) test program for selecting cyclic voltammetry, with electric current feelings of the computer monitor working electrode in the case where centainly sweeping speed
Condition.Last to calculate electrochemical surface area according to the data measured and corresponding formula, mass activity and activity specific come
Evaluate the Oxidation of Formic Acid performance of catalyst.
The beneficial effect of palladium ruthenium nanometer thorn assembling body catalyst provided by the present invention and preparation method thereof is mainly reflected in:
(1) preparation method is simple and mild, and one-step method directly obtains product, and nanometer thorn-like products collection efficiency is high.
(2) pattern and structure that can control palladium ruthenium by the concentration and volume that change presoma, thus in Oxidation of Formic Acid
Performance in is different.
(3) the palladium ruthenium nanometer thorn assembly elctro-catalyst synthesized presents outstanding active and steady in Oxidation of Formic Acid reaction
Qualitative, palladium-based materials have very high application prospect as elctro-catalyst.
(4) Detailed description of the invention
Fig. 1 is the SEM figure of 1 palladium ruthenium nanometer of specific embodiments of the present invention thorn assembling body catalyst.
Fig. 2 is TEM and the HRTEM figure of 1 palladium ruthenium nanometer of specific embodiments of the present invention thorn assembling body catalyst.
Fig. 3 is the XRD diagram of 1 palladium ruthenium nanometer of specific embodiments of the present invention thorn assembling body catalyst.
Fig. 4 is 1 palladium ruthenium nanometer of specific embodiments of the present invention thorn assembling body catalyst in 0.5M H2Following in SO4 solution
Ring volt-ampere curve.
Fig. 5 is H of 1 palladium ruthenium nanometer of the specific embodiments of the present invention thorn assembling body catalyst in 0.5M2SO4's and 0.5M
Cyclic voltammetry curve in HCOOH mixed solution.
Fig. 6 is polarogram current time of 1 palladium ruthenium nanometer of the specific embodiments of the present invention thorn assembling body catalyst at 0.3V
Curve.
Fig. 7 is that the SEM of 2 palladium ruthenium flower-like nanometer particle of specific embodiments of the present invention schemes.
Fig. 8 is the short grained SEM figure of 3 palladium ruthenium nanometer of specific embodiments of the present invention.
Fig. 9 is that the SEM of 4 palladium ruthenium polyhedral nano particles of specific embodiments of the present invention schemes.
Figure 10 is the cyclic voltammetry curve of 4 palladium ruthenium polyhedral nano particles of specific embodiments of the present invention.
(5) specific embodiment
The present invention is described further combined with specific embodiments below, but protection scope of the present invention is not limited in
This:
Referring to Fig.1~Figure 10, in the present embodiment, the performance test to the Oxidation of Formic Acid of the palladium ruthenium material is in CHI
It is carried out on 660E electrochemical workstation, operating process are as follows:
The first step weighs the sample dispersion of 2mg in 1mL ultrapure water, and ultrasound obtains uniform dispersion liquid in 60 minutes, takes 5 μ
The Nafion solution (0.5wt%) that L drop drips 5 μ L after glassy carbon electrode surface, 50 DEG C of dryings is covered on catalyst surface, is made
Working electrode.Platinum electrode is used as to electrode simultaneously, and Ag/AgCl electrode is aoxidized as reference electrode composition three-electrode system
Reduction test；
Second step selects the test program of cyclic voltammetry and polarogram current time method, with computer monitor working electrode
Current conditions in the case where centainly sweeping speed.It is last to calculate electrochemical surface area, matter according to the data measured and corresponding formula
Amount activity evaluates the Oxidation of Formic Acid performance of catalyst with activity specific.
Embodiment 1
A kind of preparation method of palladium ruthenium nanometer thorn assembling body catalyst, described method includes following steps:
1) the chlorine palladium acid sodium and ruthenic chloride for being respectively 20mM with concentration, the hydrochloric acid solution and concentration that concentration is 6M are 0.1M's
Ascorbic acid solution；
2) it takes 0.4mL chlorine palladium acid sodium and 2.6mL chlorination ruthenium solution to mix respectively, 0.1 mL hydrochloric acid solution is then added, then
The F127 of 80mg potassium bromide and 50mg is added, ultrasonic mixing is uniform；Finally add 2mL ascorbic acid solution, ultrasonic mixing 10
Minute；
3) it after solution is sufficiently mixed, is placed in oil bath pan after being heated to 90 DEG C, reaction 1 hour, washing, centrifugation, drying obtain
Assembling body catalyst is pierced to the palladium ruthenium nanometer.
The SEM figure of the palladium ruthenium nanometer thorn assembling body catalyst of acquisition is referring to Fig. 1.The palladium ruthenium nanometer thorn assembly catalysis of acquisition
The TEM figure of agent is referring to fig. 2.The XRD diagram of the palladium ruthenium nanometer thorn assembling body catalyst of acquisition is referring to Fig. 3.The palladium ruthenium nanometer of acquisition is pierced
Body catalyst is assembled in 0.5M H2SO4Cyclic voltammetry curve in solution is referring to fig. 4.The palladium ruthenium nanometer thorn assembly catalysis of acquisition
The H in 0.5 M of agent2SO4With the cyclic voltammetry curve in the HCOOH mixed solution of 0.5M referring to Fig. 5.The palladium ruthenium nanometer of acquisition
Polarogram current-time curvel of the thorn assembling body catalyst at 0.3V is referring to Fig. 6.
By SEM figure as it can be seen that the yield of palladium ruthenium nanometer thorn assembly is close to 100%, each particle hyperbranchedization, by mistake
The nanometer thorn composition three-dimensional structure fallen, nanometer thorn extend to all directions by center.Pass through HRTEM and XRD analysis, the material
The alloying level of material is good, and Pd-Ru alloy is formed.Pass through the H in 0.5M2SO4Cyclic voltammetry curve in solution can calculate
Palladium ruthenium nanometer, which pierces assembly, has very big active area, about 42.8m2g-1.According to the H in 0.5M2SO4With the HCOOH of 0.5M
Cyclic voltammetry curve in mixed solution, which can calculate palladium ruthenium nanometer thorn assembly, has very high Oxidation of Formic Acid activity, quality
Activity is 1.10A mg-1Pd, area activated is 3.32 mA cm-2.It can from the polarogram current-time curvel at 0.3V
Out, palladium ruthenium nanometer thorn assembling body catalyst has good stability.
Embodiment 2
A kind of preparation method of palladium ruthenium nanometer thorn assembling body catalyst, described method includes following steps:
1) the chlorine palladium acid sodium and chlorination ruthenium solution for being respectively 20mM with concentration, the hydrochloric acid solution and concentration that concentration is 6M are
The ascorbic acid solution of 0.1M；
2) it takes 1.5mL chlorine palladium acid sodium and 1.5mL chlorination ruthenium solution to mix respectively, 0.1 mL hydrochloric acid solution is then added, then
The F127 of 80mg potassium bromide and 50mg is added, ultrasonic mixing is uniform.Finally add 2mL ascorbic acid solution, ultrasonic mixing 10
Minute；
3) it after solution is sufficiently mixed, is placed in oil bath pan and is heated to 90 DEG C, after reacting 1 hour, washing, centrifugation, drying,
Obtain the palladium ruthenium nanometer thorn assembling body catalyst.
The SEM figure of palladium ruthenium flower-like nanometer particle is obtained referring to Fig. 7.
Schemed by SEM as it can be seen that palladium ruthenium flower-like nanometer particle is formed.This is mainly due to the ratios for changing presoma to lead to palladium
Ruthenium pattern changes.
Embodiment 3
A kind of preparation method of palladium ruthenium nanometer thorn assembling body catalyst, described method includes following steps:
1) the chlorine palladium acid sodium and ruthenic chloride for being respectively 20mM with concentration, the hydrochloric acid solution and concentration that concentration is 6M are 0.1M's
Ascorbic acid solution；
2) it takes 0.2mL chlorine palladium acid sodium and 2.8mL chlorination ruthenium solution to mix respectively, 0.2 mL hydrochloric acid solution is then added, then
The F127 of 80mg potassium bromide and 50mg is added, ultrasonic mixing is uniform.Finally add 2mL ascorbic acid solution, ultrasonic mixing 10
Minute；
3) it after solution is sufficiently mixed, is placed in oil bath pan after being heated to 90 DEG C, reaction 1 hour, washing, centrifugation, drying obtain
Assembling body catalyst is pierced to the palladium ruthenium nanometer.
The short grained SEM figure of palladium ruthenium nanometer is obtained referring to Fig. 8.
Schemed by SEM as it can be seen that palladium ruthenium nanometer little particle is formed.This is mainly due to the ratios for changing presoma to lead to palladium ruthenium
Pattern changes.
Embodiment 4
A kind of preparation method of palladium ruthenium nanometer thorn assembling body catalyst, described method includes following steps:
1) the chlorine palladium acid sodium solution for being 20mM with concentration, the ascorbic acid that the hydrochloric acid solution and concentration that concentration is 6M are 0.1M
Solution；
2) 3.0mL chlorine palladium acid sodium solution is taken, 0.2mL hydrochloric acid solution is then added, adds 80 mg potassium bromide and 50mg
F127, ultrasonic mixing is uniform, finally adds 2mL ascorbic acid solution, and ultrasonic mixing 10 minutes；
3) it after solution is sufficiently mixed, is placed in oil bath pan after being heated to 90 DEG C, reaction 1 hour, washing, centrifugation, drying obtain
To palladium polyhedral nano particles.
The SEM figure of palladium polyhedral nano particles is obtained referring to Fig. 9, obtains the cyclic voltammetry curve of palladium polyhedral nano particles
Referring to Figure 10.
Embodiment 5
A kind of preparation method of palladium ruthenium nanometer thorn assembling body catalyst, described method includes following steps:
1) the ruthenic chloride sodium solution for being 20mM with concentration, the ascorbic acid that the hydrochloric acid solution and concentration that concentration is 6M are 0.1M
Solution；
2) 3.0mL chlorination ruthenium solution is taken, 0.2mL hydrochloric acid solution is then added, adds 80mg potassium bromide and 50mg
F127, ultrasonic mixing is uniform, finally adds 2mL ascorbic acid solution, and ultrasonic mixing 10 minutes；
3) it after solution is sufficiently mixed, is placed in oil bath pan after being heated to 90 DEG C, reaction 1 hour, washing, centrifugation, drying obtain
To ruthenium nanometer little particle.
Since in this process, the more difficult reduction of ruthenic chloride, the speed of reduction is excessively slow, therefore can only obtain ruthenium and receive
Rice little particle.
Embodiment 6
A kind of preparation method of palladium ruthenium nanometer thorn assembling body catalyst, described method includes following steps:
1) the chlorine palladium acid sodium and chlorination ruthenium solution for being respectively 30mM with concentration, the hydrochloric acid solution and concentration that concentration is 10M are
The ascorbic acid solution of 0.5M；
2) it takes 0.4mL chlorine palladium acid sodium and 2.6mL chlorination ruthenium solution to mix respectively, 0.5 mL hydrochloric acid solution is then added, then
The F127 of 0.5g potassium bromide and 0.5g is added, ultrasonic mixing is uniform, finally adds 10mL ascorbic acid solution, ultrasonic mixing 30
Minute；
3) it after solution is sufficiently mixed, is placed in oil bath pan and is heated at reflux to 130 DEG C, after reaction 3 hours, washing, is done centrifugation
It is dry, obtain the palladium ruthenium nanometer thorn assembling body catalyst.
Due in this process, the concentration of chlorine palladium acid sodium and ruthenic chloride catalyst granules that is very big, therefore being synthesized
Also bigger；In addition after the amount for increasing hydrochloric acid, the reducing power of ascorbic acid can be greatly reduced, keep it more difficult for chlorine palladium acid
Sodium and ruthenic chloride reduction, therefore it is more difficult to get expected palladium ruthenium nanometer thorn assembling body catalyst.
Embodiment 7
A kind of preparation method of palladium ruthenium nanometer thorn assembling body catalyst, described method includes following steps:
1) the chlorine palladium acid sodium and chlorination ruthenium solution for being respectively 1mM with concentration, the hydrochloric acid solution and concentration that concentration is 1M are
The ascorbic acid solution of 0.01M；
2) it takes 0.4mL chlorine palladium acid sodium and 2.6mL chlorination ruthenium solution to mix respectively, 0.1 mL hydrochloric acid solution is then added, then
The F127 of 0.01g potassium bromide and 0.01g is added, ultrasonic mixing is uniform, finally adds 1mL ascorbic acid solution, ultrasonic mixing 5
Minute；
3) it after solution is sufficiently mixed, is placed in oil bath pan after being heated to 70 DEG C, reaction 0.1 hour, washing, centrifugation, drying,
Obtain the palladium ruthenium nanometer thorn assembling body catalyst.
Due in this process, the concentration of chlorine palladium acid sodium and ruthenic chloride catalyst granules that is very low, therefore being synthesized
Very little is difficult to be centrifuged out from solution, and potassium bromide and the amount of F127 are also fewer, is difficult to regulate and control the pattern of catalyst,
Moreover, reaction temperature is relatively low, it is more difficult to restore ruthenic chloride, therefore be more difficult to get expected palladium ruthenium nanometer thorn assembly catalysis
Agent.
Claims (3)
1. a kind of palladium ruthenium nanometer thorn assembling body catalyst, prepares by the following method:
(1) molten with chlorine palladium acid sodium and chlorination ruthenium solution, concentration hydrochloric acid 1~10M between of the concentration between 1~30mM respectively
The ascorbic acid solution of liquid and concentration between 0.01~0.5M；
(2) the chlorine palladium acid sodium and the mixing of chlorination ruthenium solution that total volume is 3.0mL are taken respectively, and 0.1~0.5mL is then added and has prepared
Hydrochloric acid solution, add the potassium bromide and F127 between 0.01~0.5g, be uniformly mixed；Finally add the anti-of 1~10mL
Bad hematic acid solution, ultrasonic mixing 5~30 minutes；
(3) it after solution is sufficiently mixed, is placed in oil bath pan and is heated between 70~130 DEG C, after reaction 0.1~3 hour, washing,
Centrifugation, drying obtain the palladium ruthenium nanometer thorn assembling body catalyst.
2. a kind of preparation method of palladium ruthenium nanometer thorn assembling body catalyst as described in claim 1, which is characterized in that the side
Method includes the following steps:
(1) molten with chlorine palladium acid sodium and chlorination ruthenium solution, concentration hydrochloric acid 1~10M between of the concentration between 1~30mM respectively
The ascorbic acid solution of liquid and concentration between 0.01~0.5M；
(2) the chlorine palladium acid sodium and the mixing of chlorination ruthenium solution that total volume is 3.0mL are taken respectively, and 0.1~0.5mL is then added and has prepared
Hydrochloric acid solution, add the potassium bromide and F127 between 0.01~0.5g, be uniformly mixed；Finally add the anti-of 1~10mL
Bad hematic acid solution, ultrasonic mixing 5~30 minutes；
(3) it after solution is sufficiently mixed, is placed in oil bath pan and is heated between 70~130 DEG C, after reaction 0.1~3 hour, washing,
Centrifugation, drying obtain the palladium ruthenium nanometer thorn assembling body catalyst.
3. method according to claim 2, which is characterized in that control chlorine palladium acid sodium, ruthenic chloride and ascorbic acid concentration and
The amount of volume, potassium bromide and F127, and the temperature and time of reaction control the pattern and structure of palladium ruthenium.
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Cited By (2)
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| CN111013581A (en) * | 2019-11-20 | 2020-04-17 | 浙江工业大学 | Electro-catalytic nitrogen reduction palladium-ruthenium nanorod self-assembly and controllable preparation method thereof |
| CN111785981A (en) * | 2020-06-30 | 2020-10-16 | 青岛大学 | Palladium-palladium-tungsten-chromium nano catalyst and preparation method and application thereof |
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