CN109167078A - The preparation method and applications of catalyst for fuel cell - Google Patents
The preparation method and applications of catalyst for fuel cell Download PDFInfo
- Publication number
- CN109167078A CN109167078A CN201810917566.9A CN201810917566A CN109167078A CN 109167078 A CN109167078 A CN 109167078A CN 201810917566 A CN201810917566 A CN 201810917566A CN 109167078 A CN109167078 A CN 109167078A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- heat treatment
- fuel cell
- solution
- coaupd
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- 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
- H01M4/928—Unsupported catalytic particles; loose particulate catalytic materials, e.g. in fluidised state
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inert Electrodes (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to the preparation method of a kind of fuel-cell catalyst, the post-processings and its application of catalyst.Synthetic method uses continuous reduction and co-reducing process, continuous reduction includes the following steps: that P123 and cobalt chloride is taken to dissolve, sodium borohydride solution is added dropwise after leading to nitrogen into mixed solution, again to the mixed solution that gold chloride and potassium chloropalladate are added dropwise in reaction solution, by reaction solution centrifugation, wash up to catalyst for fuel cell；Co-reducing process includes the following steps: that the mixed solution of cobalt chloride, gold chloride and potassium chloropalladate is added dropwise after sodium borohydride solution is added in logical nitrogen after taking P123 to dissolve.Metal salt, protective agent and reducing agent dosage, can obtain catalyst for fuel cell.The present invention combines two kinds of catalyst post-processing approach, and gained catalyst has good dispersibility, excellent catalytic activity and structural stability, be a kind of catalyst for fuel cell of great development prospect after heat treatment and removal alloying.
Description
Technical field
The invention belongs to field of fuel cell technology, are related to the preparation methods such as synthesis and the post-processing of catalyst, especially
It is synthesis, heat treatment and the removal alloying for relating to a types of fuel cells ternary CoAuPd catalyst.
Background technique
Chemical energy in fuel is directly converted into electric energy by electrode reaction by fuel cell, and reaction process is not related to firing
It burns, energy conversion efficiency is not limited by Carnot cycle, not will lead to energy crisis, environmental pollution, global warming and haze
Etc. environmental problems.Direct methanol fuel cell is using methanol as battery fuel, and raw material sources are abundant, cheap, storage is transported
Convenient, low noise and response are fast, are the mainstream power supplys of future fuel battery.Pt catalyst is in fuel cell and Industrial Catalysis etc.
Field is widely used, but Pt reserves are few, dosage is big, price, easily poison, and stability is not high and there are fuel infiltrations
Problem.Pd reserves are 50 times of Pt, cheap and possess and the comparable catalytic activity of Pt.Therefore, as the replacement of Pt, Pd base
Catalyst is also furtherd investigate.Although Pd has high initial activity and a low CO Poisoning Phenomenon, but its catalytic activity and steady
It is qualitative still to be improved.So the catalyst for developing high activity and high stability is fuel cell on the basis of pure Pd catalyst
The key content of research field.
Au is added in Pd catalyst is embedded in the lattice of Au in Pd, can significantly improve the stability of catalyst, and
Reduce the dosage of Pd.Due to alloy effect and difunctional mechanism, the catalytic performance of binary PdAu catalyst is far superior to pure Pd
Catalyst.Heat treatment is that one kind is commonly used to removal catalyst surface coverture (being added in synthesis process), control alloying journey
Spend and cause the common method of surface reconstruction.Catalyst is under vacuum annealing and heat treatment condition, it may occur that atomic migration
And surface segregation, the special constructions such as core-shell structure and intermetallic compound can be made, and the crystallization of catalyst can also be enhanced
Degree, alloying level and structural stability, the elongation strain effect of intermetallic compound also have a certain upgrade to catalytic performance.
Heat treatment condition includes that temperature and time has decisive influence, heat-treating atmosphere to structure-activity-stabilization sexual intercourse of catalyst
(reducing atmosphere H2, inert atmosphere N2With Ar gas, air) also have an impact to the state of oxidation and degree of segregation of catalyst surface,
So as to cause the change of final catalytic performance.
A kind of post-processing approach of the removal alloying as catalyst, can reconstruct catalyst surface, improve point of catalyst
Property is dissipated, catalyst surface in reaction process is removed and adsorbs remaining protective agent (such as P123) and pattern controlling agent (such as KI),
Also it can change structure-activity-stabilization sexual intercourse of catalyst.Removal alloying method is divided into chemical removal alloying again and electrochemistry is gone
Alloying, during chemical removal alloying, base metal is dissolved from alloy, and the noble metal that left behind forms self-organizing
Open celled foam shape nano-porous structure.Relatively, electrochemistry removal alloying then will form coarse Pd clad, prevent catalyst
The alloy of internal layer further dissolves out, and forms the special core-shell structure with shell and Pd based alloy core rich in Pd, this special
Core-shell structure can further enhance catalytic performance.Result after removal alloying is usually showing higher methanol oxidation and oxygen also
Former activity, but structural stability has a degree of decline, and the catalytic performance and structural stability of catalyst can pass through heat
The methods of processing and vacuum annealing improve.
The present invention is being respectively synthesized out hollow structure and reality using continuous reduction (potential replacement reaction) and co-reducing process
On the basis of the ternary CoAuPd alloy catalyst of core structure, to further increase its catalytic performance and structural stability, to it
Heat treatment and removal alloying are carried out, two kinds of post-processing approach are combined, are learnt from other's strong points to offset one's weaknesses.The knot of catalyst is improved by heat treatment
Structure stability and catalytic activity, then the base metal of catalyst surface is dissolved away by removal alloying, increase electro-chemical activity face
Long-pending and reactivity site increases dispersibility and reduces caused reunion in heat treatment process, catalytic performance improved, to make
The catalyst for fuel cell of standby high activity and high stability out.
Summary of the invention
It is an object of the invention to control reaction condition and step synthesis to have the ternary of hollow structure and solid construction
CoAuPd alloy nano catalyst improves the structural stability and durability of catalyst by heat treatment, then by removing alloy
Change method improves the dispersibility of catalyst, reduces and reunite and improve catalytic performance, to prepare high activity and high stability
Catalyst.
To realize the above purposes, the technical scheme adopted is as follows:
The synthesis of one types of fuel cells ternary CoAuPd alloy catalyst uses continuous reduction and co-reducing process, even
In continuous reduction method, first with reducing agent NaBH4Synthesize Co nano particle, the mixing of gold chloride and potassium chloropalladate is then added dropwise
Using the difference of the reduction potential of Co and Au, Pd potential replacement reaction occurs for solution, i.e. Co displaces Au and Pd element, passes through
Continuous reduction and potential replacement reaction are easy to synthesize the catalyst with hollow structure.Coreduction rule is to protection
Agent P123 and reducing agent NaBH4Mixed solution in, be added dropwise tri- kinds of metal precursors of Co, Au and Pd mixed solution so that three
Coreduction occurs for kind metal salt, to synthesize the alloy catalyst of solid construction.
, Pd/C catalyst black compared to corresponding binary PdAu catalyst and business Pd, ternary CoAuPd catalyst have more
Excellent catalytic activity, better stability and durability, this makes ternary CoAuPd catalyst in fuel cell and correlation
The great development prospect of catalytic field and application value.Therefore implement various post-processing sides on the basis of ternary CoAuPd catalyst
Method attempts the catalytic performance for being further improved catalyst.Specifically, heat treatment and removal alloying are implemented to catalyst, and will
Two kinds of post-processing approach combine, i.e., further implement removal alloying after implementing heat treatment to catalyst.It is mentioned using heat treatment
The structural stability of high catalyst recycles removal alloying to improve the catalytic activity of catalyst, increases the dispersibility of catalyst, subtract
Caused agglomeration in few heat treatment process, finally prepares the catalyst of high activity and high stability.
Method includes the following steps:
(1) synthetic method of catalyst includes continuous reduction and co-reducing process；Continuous reduction: to P123 solution (1~
Cobalt chloride solution (0.01~1mmol/L) is added in 1000mg/mL), entire reaction process one leads directly to nitrogen and magnetic agitation, instead
It answers temperature control at 0~180 DEG C, is slowly added dropwise sodium borohydride solution (0.1~50mg/mL), rate of addition is 1~10s/ drop；
After reacting 30~60min, after the sodium borohydride in solution has hydrolyzed, gold chloride (0.01~1mmol/L) and chlorine is slowly added dropwise
The mixed solution of palladium acid potassium (0.01~1mmol/L), rate of addition are 1~10s/ drop, after dripping the reaction was continued 4~12h afterwards
Stop reaction.Reaction solution centrifuge separation, secondary distilled water and dehydrated alcohol are washed 3~5 times up to catalyst for fuel cell.
Co-reducing process: a straight-through N in P123 solution (1~1000mg/mL)2And be stirred continuously, it is subsequently poured into sodium borohydride solution
(0.1~50mg/mL) immediately begins to that cobalt chloride (0.01~1mmol/L), gold chloride (0.01~1mmol/L) and chlorine palladium is added dropwise
The mixed solution of sour potassium (0.01~1mmol/L).Remaining reaction condition and laboratory operating procedures are consistent with continuous reduction, can obtain
Catalyst for fuel cell.
(2) post-processing approach of catalyst includes heat treatment and removal alloying.Heat treatment method: the catalyst of synthesis is put
Enter in vacuum drying oven dry, and is ground to agate mortar powdered, is dispersed on porcelain boat and is put into tube furnace and carry out
Heat treatment.It is vacuumized before heat treatment 3~5 times, inert gas (such as Ar and N is led in heat treatment process2) etc. protection, take program
Heating, heating rate are 1~5 DEG C/min, and heat treatment temperature is 100~1000 DEG C, and heat treatment time is 1~12h.It has been heat-treated
Room temperature is naturally cooled to after finishing, grinds and disperses in ethanol to get the catalyst after heat treatment.Removal alloying method includes changing
Learn removal alloying and electrochemistry removal alloying: chemical removal alloying will be heat-treated after catalyst soak in 0.01~1.0M
H2SO4In solution, ultrasound is uniformly mixed it, uses second distillation water washing 3~5 times after impregnating 1~12h.Electrochemistry removal alloying
Catalyst after will being heat-treated is coated on working electrode (GC electrode), and electro-chemical test instrument is AUTOLAB electrochemical operation
Stand (PGSTAT12), and test temperature is room temperature (10~50 DEG C).It is after plating platinum black to electrode using the three-electrode system of standard
Platinized platinum (1cm × 1cm), reference electrode are saturated calomel electrode (SCE).Using cyclic voltammetry, in 0.01~1.0M H2SO4It is molten
Cyclic voltammetry is carried out in liquid.Scanning potential windows be -0.2V~0.9V, sweep speed be 1~1000mV/s, scanning circle number be 1~
100 circles.By the catalyst after heat treatment to get urging after heat treatment and removal alloying after two kinds of removal alloying methods are handled
Agent.
Further preferably, in the continuous reduction of step (1), triblock copolymer P123 concentration is 10mg/mL, chlorination
Cobalt concentration is 0.1mmol/L, and sodium borohydride concentration is 10mg/mL, and sodium borohydride solution rate of addition is controlled in 5s/ drop.It is added dropwise
After complete 40min, then the mixed solution of gold chloride and potassium chloropalladate is slowly added dropwise, potassium chloropalladate concentration is 0.03mmol/L, chlorine gold
Acid concentration is 0.03mmol/L, drips speed control in 5s/ drop.Stop reaction after reacting 4~12h, by reaction solution centrifuge separation, ultrasound
Washing and dehydrated alcohol wash 3~5 times to get catalyst for fuel cell.In the co-reducing process of step (1), triblock copolymer
Object P123 concentration be 10mg/mL, pour into sodium borohydride solution concentration be 10mg/mL, be then slowly added dropwise cobalt chloride, gold chloride and
The mixed solution of potassium chloropalladate, cobalt chloride concentration 0.03mmol/L, gold chloride concentration are 0.03mmol/L, potassium chloropalladate concentration
For 0.03mmol/L, speed control is dripped in 5s/ drop.Remaining reaction condition and experimental procedure are consistent with continuous reduction, can obtain fuel
Battery catalyst.
It in the heat treatment process of step (2), is vacuumized before heat treatment, Ar gas shielded, temperature programming is led in heat treatment process
Rate is 2 DEG C/min, and heat treatment temperature is 300 DEG C, and heat treatment time 2h naturally cools to room temperature after heat treatment, grinds
It grinds and disperses in ethanol to get the catalyst for fuel cell after heat treatment.In the removal alloying step of step (2), chemistry
Removal alloying is 0.1M H2SO412h is impregnated in solution, is then used second distillation water washing 3 times.Electrochemistry removal alloying is 0.1M
H2SO4Cyclic voltammetry scan in solution, potential windows are -0.2V~0.9V, and sweeping speed is 100mV/s, and scanning circle number is 60 circles.It will be hot
Treated catalyst is after removal alloying to get the catalyst for fuel cell after heat treatment and removal alloying.
The fuel-cell catalyst is the nano particle with hollow structure and solid construction.
The fuel-cell catalyst electrochemical surface area (ECSA) is 1~1000m2/gPd。
The preparation method and applications of types of fuel cells high activity and high stability catalyst according to the present invention,
There is following outstanding feature:
(1) synthetic method includes continuous reduction and co-reducing process, and P123 makees protective agent and NaBH4Make reducing agent, is easy to
Hollow structure (potential replacement reaction) and solid construction nano particle are synthesized, reaction condition is mild, and it is green and pollution-free, it is easy to
Large-scale production.Hollow structure is due to inside and outside two layers of surface, and two surfaces can play catalytic action, make its catalysis
Performance is far superior to the solid construction under equal conditions.
(2) it is firstly introduced into Au, reduces precious metals pd dosage, form binary PdAu alloy, utilize alloy effect and difunctional
The catalytic activity and structural stability of mechanism raising catalyst.It is re-introduced into Co and further decreases noble metal dosage, form ternary
CoAuPd alloy catalyst., Pd/C catalyst black compared to binary PdAu catalyst and business Pd, ternary CoAuPd catalyst have
Better catalytic activity, stability and durability.
(3) after heat treatment, crystallinity, alloying level and the structural stability of catalyst obtain ternary CoAuPd catalyst
To further increasing.Moreover, heat treatment is so that catalyst becomes ordered structure and intermetallic compound from unordered alloy state
Equal special constructions, the elongation strain effect of intermetallic compound also have a certain upgrade to the catalytic performance of catalyst.
(4) removal alloying can dissolve away the transition metal Co in ternary CoAuPd catalyst, form rough surface and possess more greatly
Specific surface area, more defect sites and reactivity site are exposed, electrochemical surface area increases, and removal alloying energy
Increase the dispersibility of catalyst, reduces caused reunion in heat treatment process.Therefore the ternary CoAuPd catalyst after being heat-treated
After removal alloying, possess better dispersibility, higher catalytic performance and superior structural stability.
(5) ternary CoAuPd alloy catalyst is after electrochemistry removal alloying, become to have CoAuPd alloy core and
The CoAuPd AuPd core-shell structure of coarse AuPd alloy shell, this special core-shell structure enhance catalytic performance.It is empty
Core structure catalyst can carry out electrochemistry removal alloying due to inside and outside two layers of surface, formed inside and outside two layers it is coarse
AuPd alloy shell.Therefore, hollow structure evolves into hollow porous CoAuPd@AuPd structure after electrochemistry removal alloying, urges
Change performance to improve a lot again on the basis of hollow structure early period.Moreover, hollow porous CoAuPd@AuPd structured catalysis
The general CoAuPd@AuPd structure formed by solid construction and initial solid construction and hollow structure can be better than.
(6) heat treatment can remove surfactant that during synthetic catalyst catalyst surface adsorbs (such as P123,
PVP and F127 etc.), so that the catalyst with clean surface is obtained, due to occupying protectant removal of active site,
So that the catalyst with clean surface possesses more active sites, bigger specific surface area and electrochemical surface area
(compared to the state before heat treatment).In addition to this, removal alloying can dissolve away the transition metal Co of catalyst surface, and be adsorbed on and urge
The surfactant on agent surface can also remove therewith, therefore removal alloying method can also obtain the catalysis with clean surface
Agent.
(7) for ternary CoAuPd alloy catalyst after Overheating Treatment and removal alloying, obtained catalyst structure is steady
Qualitative and catalytic performance has biggish promotion, has excellent alcohols catalysis oxidation and hydrogen reduction performance, leads in fuel cell
There are biggish application value and development prospect in domain, Industrial Catalysis field and large-scale commercial.What the technical program was related to
The synthesis and modification of catalyst: then synthetic catalyst first is combined with various post-processing approach, is promoted and is improved catalyst
Catalytic activity and stable structure；This scheme can also be used for similar and related fields catalyst and nano material preparation and
It improves.
Using technical solution of the present invention synthesis ternary Pd base catalyst component selection, control synthesis, surface regulation,
Catalytic performance and structural stability, which adjust aspect, bigger operating space, and catalytic activity is far superior to corresponding binary and closes
Au catalyst and commercial catalysts.On this basis, heat treatment and removal alloying are carried out to catalyst, further increases catalyst
Structural stability and catalytic activity, be made and possess the catalyst for fuel cell of high activity and high stability.The technical program
Since simple synthetic method is easy, it is easy to be mass produced, the post-processing approach phase of heat treatment and two kinds of catalyst of removal alloying
In conjunction with learning from other's strong points to offset one's weaknesses；On the basis of synthesizing the ternary CoAuPd catalyst of high catalytic activity and stability, apply post-processing to it
Catalytic activity and stability further progress are improved.The technical program novelty degree is higher, innovative stronger, can be applied to Pt base,
Synthesis, structure and the performance regulation of the associated catalysts such as Pd base catalyst and industrial catalyst and nano material and catalytic
The improvement of energy.
Detailed description of the invention
Fig. 1: for transmission electron microscope Fig. 1 of the catalyst after the heat treatment of fuel cell prepared by embodiment 1.
Fig. 2: it is being heat-treated and the methanol after electrochemistry removal alloying for catalyst for fuel cell prepared by embodiment 1
Oxidation susceptibility test, wherein a is cyclic voltammetry curve and CO adsorption curve of the catalyst in 1.0M NaOH solution；B is to urge
Agent is in 1.0M NaOH+1.0M CH3Accelerated ageing test (500 circle cyclic voltammetry scan) in OH solution；C and d are respectively
Corresponding j-t curve and performance degradation curve.
Fig. 3: for transmission electron microscope Fig. 3 of the catalyst after the heat treatment of fuel cell prepared by embodiment 2.
Fig. 4: it is being heat-treated and the methanol after electrochemistry removal alloying for catalyst for fuel cell prepared by embodiment 2
Oxidation susceptibility test, wherein a is cyclic voltammetry curve and CO adsorption curve of the catalyst in 1.0M NaOH solution；B is to urge
Agent is in 1.0M NaOH+1.0M CH3Accelerated ageing test (500 circle cyclic voltammetry scan) in OH solution；C and d is corresponding
J-t curve and performance degradation curve.
Fig. 5: being catalyst for fuel cell prepared by embodiment 2 in the case where heat treatment time is 1h, different heat treatment temperature
XRD diagram 5 under degree.
Fig. 6: being catalyst for fuel cell prepared by embodiment 2 in the case where heat treatment time is 2h, different heat treatment temperature
XRD diagram 6 under degree.
Specific embodiment
It is arranged with reference to the accompanying drawing with specific implementation case, the present invention is further explained, it should be understood that these embodiments are only used for
It is bright the present invention rather than limit the scope of the invention, after the present invention has been read, those skilled in the art are to of the invention
The modification of various equivalent forms falls within the application range as defined in the appended claims.
Embodiment 1
(1) it takes 1.0g P123 to be dissolved in 30mL secondary distilled water, takes 0.022g CoCl2·6H2O is dissolved in 20mL bis- times steamings
In distilled water, then above two solution is uniformly mixed, is poured into round-bottomed flask and magnetic agitation.Nitrogen is passed through before reaction
30min, reaction temperature are controlled at room temperature (30 DEG C).Take 0.1g NaBH4It is dissolved in 20mL secondary distilled water, and with the speed of 5s/ drop
Spend the mixed solution and dripping to P123 and cobalt chloride.
(2) after being added dropwise, to NaBH after reaction 50min4After having hydrolyzed, it is added dropwise into reaction solution with the speed of 5s/ drop
The mixed solution of 20mL gold chloride (0.03mmol/L) and potassium chloropalladate (0.03mmol/L).Stop reaction after 4h, by reaction solution
Centrifuge separation, products therefrom is with secondary distilled water centrifuge washing 3 times, then with dehydrated alcohol centrifuge washing 3 times to get fuel cell
Use catalyst.
(3) catalyst of synthesis is placed in vacuum drying oven drying, is ground to agate mortar powdered, be dispersed in
On porcelain boat and it is put into tube furnace and is heat-treated.It is vacuumized before heat treatment 3 times, Ar gas shielded is passed through in heat treatment process, is adopted
Program fetch heating, heating rate are 2 DEG C/min, and heat treatment temperature is 300 DEG C, heat treatment time 2h.Then it naturally cools to
Room temperature is ground and is dispersed in ethanol to get the catalyst after heat treatment.
(4) catalyst after heat treatment is coated on glass-carbon electrode as working electrode, using cyclic voltammetry to its into
The test of row electrochemistry removal alloying: electro-chemical test instrument is AUTOLAB electrochemical workstation (PGSTAT12), and test temperature is
Room temperature (30 DEG C).It is the platinized platinum (1cm × 1cm) after plating platinum black to electrode, reference electrode is full using the three-electrode system of standard
With calomel electrode (SCE).In the 0.1M H of nitrogen saturation2SO4Carry out cyclic voltammetry in solution, scanning potential be -0.2V~
0.9V (vs SCE), sweeping speed is 100mV/s, and scanning circle number is 60 circles.
(5) catalytic performance of catalyst aoxidizes test characterization, the 1.0M that methanol oxidation test is saturated in nitrogen by methanol
It is carried out in NaOH solution, using cyclic voltammetry, scanning range is -0.9V~0.5V (vs SCE), and sweeping speed is 100mV/s,
20 circle of scanning；And the 1.0M NaOH+1.0M CH in nitrogen saturation3It is carried out in OH solution, scanning range is -0.8V~0.4V
(vs SCE), sweeping speed is 50mV/s, 20 circle of scanning.
Fig. 1 show the transmission after the present embodiment preparation gained fuel cell ternary CoAuPd alloy catalyst heat treatment
Electron microscope；Catalyst occurs slightly to reunite after heat treatment it can be seen from Fig. 1 a, in figure after grain size distribution display heat treatment
The average grain diameter of catalyst is in 5.93nm or so.Due to using continuous reduction, so Fig. 1 a and b illustration shows apparent sky
Core structure.Crystal form and crystallinity increase catalyst after heat treatment, therefore, after being heat-treated it can be seen from Fig. 1 c and d
Catalyst shows very regular lattice fringe and ordered structure.
Fig. 2 show the present embodiment preparation gained fuel cell ternary CoAuPd alloy catalyst in heat treatment and electrification
Methanol oxidation susceptibility test after learning removal alloying；Fig. 2 a be cyclic voltammetry curve of the catalyst in 1.0M NaOH solution and
CO adsorption curve, Fig. 2 b are catalyst in 1.0M NaOH+1.0M CH3Accelerated ageing test (500 circle circulation volts in OH solution
Peace scanning), Fig. 2 c and d are corresponding j-t curve and performance degradation curve.Wherein, by CO absorption test catalyst in heat
Electrochemical surface area ECSA after processing and electrochemistry removal alloying is 30.114m2/gPd.It is shown under 0.0V current potential in Fig. 2 b
Methanol oxidation peak is shown, wherein the initial activity of catalyst is 1.109mA/cm2, after accelerated ageing is tested, methanol oxidation
Areal electric current density is 0.895mA/cm2, current density also surplus 80.70%, illustrating catalyst after heat treatment has well
Structural stability and catalytic stability.Fig. 2 c shows that catalyst has good antitoxinization energy in catalysis oxidation methanol process
Power, catalytic stability and durability.
Embodiment 2
(1) it takes 1.0g P123 to be dissolved in 30mL secondary distilled water and pours into round-bottomed flask and magnetic agitation, be passed through nitrogen
After 30min, 0.1g NaBH is taken4Be dissolved in 20mL secondary distilled water and directly pour into round-bottomed flask, immediately after to reaction solution with
20mL cobalt chloride (0.03mmol/L), gold chloride (0.03mmol/L) and potassium chloropalladate (0.03mmol/ is added dropwise in the speed of 5s/ drop
L mixed solution).Reaction temperature control stops reaction after reacting 4h, reaction solution is centrifugated, gained at room temperature (30 DEG C)
Product is with secondary distilled water centrifuge washing 3 times, then with dehydrated alcohol centrifuge washing 3 times to get catalyst for fuel cell.
(2) catalyst of synthesis is placed in vacuum drying oven drying, is ground to agate mortar powdered, be dispersed in
On porcelain boat and it is put into tube furnace and is heat-treated.It is vacuumized before heat treatment 3 times, Ar gas shielded is passed through in heat treatment process, is adopted
Program fetch heating, heating rate are 2 DEG C/min, and heat treatment temperature is 300 DEG C, heat treatment time 2h.Then it naturally cools to
Room temperature is ground and is dispersed in ethanol to get the catalyst after heat treatment.
(3) catalyst after heat treatment is coated on glass-carbon electrode as working electrode, using cyclic voltammetry to its into
The test of row electrochemistry removal alloying: electro-chemical test instrument is AUTOLAB electrochemical workstation (PGSTAT12), and test temperature is
Room temperature (30 DEG C).It is the platinized platinum (1cm × 1cm) after plating platinum black to electrode, reference electrode is full using the three-electrode system of standard
With calomel electrode (SCE).In the 0.1M H of nitrogen saturation2SO4Carry out cyclic voltammetry in solution, scanning potential be -0.2V~
0.9V (vs SCE), sweeping speed is 100mV/s, and scanning circle number is 60 circles.
(4) catalytic performance of catalyst aoxidizes test characterization, the 1.0M that methanol oxidation test is saturated in nitrogen by methanol
It is carried out in NaOH solution, using cyclic voltammetry, scanning range is -0.9V~0.5V (vs SCE), and sweeping speed is 100mV/s,
20 circle of scanning；And the 1.0M NaOH+1.0M CH in nitrogen saturation3It is carried out in OH solution, scanning range is -0.8V~0.4V
(vs SCE), sweeping speed is 50mV/s, 20 circle of scanning.
Fig. 3 show the transmission after the present embodiment preparation gained fuel cell ternary CoAuPd alloy catalyst heat treatment
Electron microscope；Being heat-treated at 300 DEG C after 2h by catalyst it can be seen from Fig. 3 a still has dispersibility well, basic to present
Monodisperse status, there is no reuniting；The average grain diameter of grain size distribution display heat treatment rear catalyst is on the left side 6.02nm in figure
It is right.Due to using co-reducing process, so Fig. 3 a and b illustration shows that catalyst is solid construction nano particle.Catalyst is in Re Chu
Crystal form and crystallinity increase after reason, and therefore, the catalyst after being heat-treated it can be seen from Fig. 3 c shows very regular
Lattice fringe and ordered structure occur the special constructions such as the intermetallic compound of atomic ordered arrangement in Fig. 3 d.
Fig. 4 show the present embodiment preparation gained fuel cell ternary CoAuPd alloy catalyst in heat treatment and electrification
Methanol oxidation susceptibility test after learning removal alloying；Fig. 4 a be cyclic voltammetry curve of the catalyst in 1.0M NaOH solution and
CO adsorption curve, Fig. 4 b are catalyst in 1.0M NaOH+1.0M CH3Accelerated ageing test (500 circle circulation volts in OH solution
Peace scanning)；Fig. 4 c and d are corresponding i-t curve and performance degradation curve.Wherein, by CO absorption test catalyst in heat
Electrochemical surface area ECSA after processing and electrochemistry removal alloying is 36.425m2/gPd.It is shown under 0.0V current potential in Fig. 4 b
Methanol oxidation peak is shown, wherein the initial activity of catalyst is 1.066mA/cm2, after accelerated ageing is tested, methanol oxidation
Areal electric current density is 0.935mA/cm2, current density also surplus 87.67%, illustrating catalyst after heat treatment has well
Structural stability and catalytic stability.Fig. 4 c shows that catalyst has good antitoxinization energy in catalysis oxidation methanol process
Power, catalytic stability and durability.
Fig. 5 and Fig. 6 show the present embodiment preparation gained fuel cell ternary CoAuPd alloy catalyst in different heat
XRD diagram under treatment conditions, Fig. 5 show catalyst (200 DEG C, 300 DEG C, 400 at a temperature of being heat-treated 1h and different heat treatment
DEG C and 500 DEG C) under XRD diagram；Fig. 6 show catalyst be heat-treated 2h and at a temperature of different heat treatment (200 DEG C, 300 DEG C,
400 DEG C and 500 DEG C) under XRD diagram.As seen from the figure, catalyst heat treatment condition is to show stronger XRD under 300 DEG C and 2h
Diffraction maximum illustrates that under this heat treatment condition, crystal form, crystallinity and the alloying level of catalyst are all greatly improved.
Embodiment 3
(1) it takes 1.0g P123 to be dissolved in 30mL secondary distilled water, takes 0.022g CoCl2·6H2O is dissolved in 20mL bis- times steamings
In distilled water, then above two solution is uniformly mixed, is poured into round-bottomed flask and magnetic agitation.Nitrogen is passed through before reaction
30min, reaction temperature are controlled at room temperature (30 DEG C).Take 0.1g NaBH4It is dissolved in 20mL secondary distilled water, and with the speed of 3s/ drop
Spend the mixed solution and dripping to P123 and cobalt chloride.
(2) after being added dropwise, to NaBH after reaction 50min4After having hydrolyzed, it is added dropwise into reaction solution with the speed of 3s/ drop
The mixed solution of 20mL gold chloride (0.03mmol/L) and potassium chloropalladate (0.03mmol/L).Stop reaction after 4h, by reaction solution
Centrifuge separation, products therefrom is with secondary distilled water centrifuge washing 3 times, then with dehydrated alcohol centrifuge washing 3 times to get fuel cell
Use catalyst.
(3) catalyst of synthesis is placed in vacuum drying oven drying, is ground to agate mortar powdered, be dispersed in
On porcelain boat and it is put into tube furnace and is heat-treated.It is vacuumized before heat treatment 3 times, N is passed through in heat treatment process2Gas shielded is adopted
Program fetch heating, heating rate are 3 DEG C/min, and heat treatment temperature is 300 DEG C, heat treatment time 1h.Then it naturally cools to
Room temperature is ground and is dispersed in ethanol to get the catalyst after heat treatment.
(4) catalyst after heat treatment is placed in the 0.1M H of 10mL2SO4In solution, ultrasonic agitation is uniformly mixed it,
Impregnate 12h.Then solution is centrifugated, with secondary distilled water centrifuge washing 3 times, disperses and be stored in dehydrated alcohol, i.e.,
It must be heat-treated and the catalyst for fuel cell after removal alloying.
(5) catalytic performance of catalyst aoxidizes test characterization, the 1.0M that methanol oxidation test is saturated in nitrogen by methanol
It is carried out in NaOH solution, using cyclic voltammetry, scanning range is -0.9V~0.5V (vs SCE), and sweeping speed is 100mV/s,
20 circle of scanning；And the 1.0M NaOH+1.0M CH in nitrogen saturation3It is carried out in OH solution, scanning range is -0.8V~0.4V
(vs SCE), sweeping speed is 50mV/s, 20 circle of scanning.
Embodiment 4
(1) it takes 1.0g P123 to be dissolved in 30mL secondary distilled water and pours into round-bottomed flask and magnetic agitation, be passed through nitrogen
After 30min, 0.1g NaBH is taken4Be dissolved in 20mL secondary distilled water and directly pour into round-bottomed flask, immediately after to reaction solution with
20mL cobalt chloride (0.03mmol/L), gold chloride (0.03mmol/L) and potassium chloropalladate (0.03mmol/ is added dropwise in the speed of 3s/ drop
L mixed solution).Reaction temperature control stops reaction after reacting 4h, reaction solution is centrifugated, gained at room temperature (30 DEG C)
Product is with secondary distilled water centrifuge washing 3 times, then with dehydrated alcohol centrifuge washing 3 times to get catalyst for fuel cell.
(2) catalyst of synthesis is placed in vacuum drying oven drying, is ground to agate mortar powdered, be dispersed in
On porcelain boat and it is put into tube furnace and is heat-treated.It is vacuumized before heat treatment 3 times, N is passed through in heat treatment process2Gas shielded is adopted
Program fetch heating, heating rate are 3 DEG C/min, and heat treatment temperature is 300 DEG C, heat treatment time 1h.Then it naturally cools to
Room temperature is ground and is dispersed in ethanol to get the catalyst after heat treatment.
(3) catalyst after heat treatment is placed in the 0.1M H of 10mL2SO4In solution, ultrasonic agitation is uniformly mixed it,
Impregnate 12h.Then solution is centrifugated, with secondary distilled water centrifuge washing 3 times, disperses and be stored in dehydrated alcohol, i.e.,
It must be heat-treated and the catalyst for fuel cell after removal alloying.
(4) catalytic performance of catalyst aoxidizes test characterization, the 1.0M that methanol oxidation test is saturated in nitrogen by methanol
It is carried out in NaOH solution, using cyclic voltammetry, scanning range is -0.9V~0.5V (vs SCE), and sweeping speed is 100mV/s,
20 circle of scanning；And the 1.0M NaOH+1.0M CH in nitrogen saturation3It is carried out in OH solution, scanning range is -0.8V~0.4V
(vs SCE), sweeping speed is 50mV/s, 20 circle of scanning.
Embodiment 5
(1) it takes 1.0g P123 to be dissolved in 30mL secondary distilled water, takes 0.022g CoCl2·6H2O is dissolved in 20mL bis- times steamings
In distilled water, then above two solution is uniformly mixed, is poured into round-bottomed flask and magnetic agitation.Nitrogen is passed through before reaction
30min, reaction temperature are controlled at room temperature (30 DEG C).Take 0.1g NaBH4It is dissolved in 20mL secondary distilled water, and with the speed of 3s/ drop
Spend the mixed solution and dripping to P123 and cobalt chloride.
(2) after being added dropwise, to NaBH after reaction 1h4After having hydrolyzed, 20mL is added dropwise with the speed of 5s/ drop into reaction solution
The mixed solution of gold chloride (0.03mmol/L) and potassium chloropalladate (0.03mmol/L).Stop reaction after 6h, reaction solution is centrifuged
Separation, products therefrom with secondary distilled water centrifuge washing 3 times, then with dehydrated alcohol centrifuge washing 3 times to get fuel cell with urging
Agent.
(3) catalyst of synthesis is placed in vacuum drying oven drying, is ground to agate mortar powdered, be dispersed in
On porcelain boat and it is put into tube furnace and is heat-treated.It is vacuumized before heat treatment 3 times, Ar gas shielded is passed through in heat treatment process, is adopted
Program fetch heating, heating rate are 2 DEG C/min, and heat treatment temperature is 400 DEG C, heat treatment time 1h.Then it naturally cools to
Room temperature is ground and is dispersed in ethanol to get the catalyst after heat treatment.
(4) catalyst after heat treatment is coated on glass-carbon electrode as working electrode, using cyclic voltammetry to its into
The test of row electrochemistry removal alloying: electro-chemical test instrument is AUTOLAB electrochemical workstation (PGSTAT12), and test temperature is
Room temperature (30 DEG C).It is the platinized platinum (1cm × 1cm) after plating platinum black to electrode, reference electrode is full using the three-electrode system of standard
With calomel electrode (SCE).In the 0.5M H of nitrogen saturation2SO4Carry out cyclic voltammetry in solution, scanning potential be -0.2V~
0.9V (vs SCE), sweeping speed is 50mV/s, and scanning circle number is 40 circles.
(5) catalytic performance of catalyst aoxidizes test characterization, the 1.0M that methanol oxidation test is saturated in nitrogen by methanol
It is carried out in NaOH solution, using cyclic voltammetry, scanning range is -0.9V~0.5V (vs SCE), and sweeping speed is 100mV/s,
20 circle of scanning；And the 1.0M NaOH+1.0M CH in nitrogen saturation3It is carried out in OH solution, scanning range is -0.8V~0.4V
(vs SCE), sweeping speed is 50mV/s, 20 circle of scanning.
Embodiment 6
(1) it takes 1.0g P123 to be dissolved in 30mL secondary distilled water and pours into round-bottomed flask and magnetic agitation, be passed through nitrogen
After 30min, 0.1g NaBH is taken4Be dissolved in 20mL secondary distilled water and directly pour into round-bottomed flask, immediately after to reaction solution with
20mL cobalt chloride (0.03mmol/L), gold chloride (0.03mmol/L) and potassium chloropalladate (0.03mmol/ is added dropwise in the speed of 5s/ drop
L mixed solution).Reaction temperature control stops reaction after reacting 6h, reaction solution is centrifugated, gained at room temperature (30 DEG C)
Product is with secondary distilled water centrifuge washing 3 times, then with dehydrated alcohol centrifuge washing 3 times to get catalyst for fuel cell.
(2) catalyst of synthesis is placed in vacuum drying oven drying, is ground to agate mortar powdered, be dispersed in
On porcelain boat and it is put into tube furnace and is heat-treated.It is vacuumized before heat treatment 3 times, Ar gas shielded is passed through in heat treatment process, is adopted
Program fetch heating, heating rate are 2 DEG C/min, and heat treatment temperature is 400 DEG C, heat treatment time 1h.Then it naturally cools to
Room temperature is ground and is dispersed in ethanol to get the catalyst after heat treatment.
(3) catalyst after heat treatment is coated on glass-carbon electrode as working electrode, using cyclic voltammetry to its into
The test of row electrochemistry removal alloying: electro-chemical test instrument is AUTOLAB electrochemical workstation (PGSTAT12), and test temperature is
Room temperature (30 DEG C).It is the platinized platinum (1cm × 1cm) after plating platinum black to electrode, reference electrode is full using the three-electrode system of standard
With calomel electrode (SCE).In the 0.5M H of nitrogen saturation2SO4Carry out cyclic voltammetry in solution, scanning potential be -0.2V~
0.9V (vs SCE), sweeping speed is 50mV/s, and scanning circle number is 40 circles.
(4) catalytic performance of catalyst aoxidizes test characterization, the 1.0M that methanol oxidation test is saturated in nitrogen by methanol
It is carried out in NaOH solution, using cyclic voltammetry, scanning range is -0.9V~0.5V (vs SCE), and sweeping speed is 100mV/s,
20 circle of scanning；And the 1.0M NaOH+1.0M CH in nitrogen saturation3It is carried out in OH solution, scanning range is -0.8V~0.4V
(vs SCE), sweeping speed is 50mV/s, 20 circle of scanning.
Embodiment 7
(1) it takes 1.0g P123 to be dissolved in 30mL secondary distilled water, takes 0.022g CoCl2·6H2O is dissolved in 20mL bis- times steamings
In distilled water, then above two solution is uniformly mixed, is poured into round-bottomed flask and magnetic agitation.Nitrogen is passed through before reaction
30min, reaction temperature are controlled at room temperature (30 DEG C).Take 0.1g NaBH4It is dissolved in 20mL secondary distilled water, and with the speed of 3s/ drop
Spend the mixed solution and dripping to P123 and cobalt chloride.
(2) after being added dropwise, to NaBH after reaction 50min4After having hydrolyzed, it is added dropwise into reaction solution with the speed of 3s/ drop
The mixed solution of 20mL gold chloride (0.03mmol/L) and potassium chloropalladate (0.03mmol/L).Stop reaction after 6h, by reaction solution
Centrifuge separation, products therefrom is with secondary distilled water centrifuge washing 3 times, then with dehydrated alcohol centrifuge washing 3 times to get fuel cell
Use catalyst.
(3) catalyst of synthesis is placed in vacuum drying oven drying, is ground to agate mortar powdered, be dispersed in
On porcelain boat and it is put into tube furnace and is heat-treated.It is vacuumized before heat treatment 3 times, N is passed through in heat treatment process2Gas shielded is adopted
Program fetch heating, heating rate are 3 DEG C/min, and heat treatment temperature is 200 DEG C, heat treatment time 2h.Then it naturally cools to
Room temperature is ground and is dispersed in ethanol to get the catalyst after heat treatment.
(4) catalyst after heat treatment is placed in the 0.5M H of 10mL2SO4In solution, ultrasonic agitation is uniformly mixed it,
Impregnate 6h.Then solution is centrifugated, with secondary distilled water centrifuge washing 3 times, disperse and be stored in dehydrated alcohol to get
Catalyst for fuel cell after heat treatment and removal alloying.
(5) catalytic performance of catalyst aoxidizes test characterization, the 1.0M that methanol oxidation test is saturated in nitrogen by methanol
It is carried out in NaOH solution, using cyclic voltammetry, scanning range is -0.9V~0.5V (vs SCE), and sweeping speed is 100mV/s,
20 circle of scanning；And the 1.0M NaOH+5.0M CH in nitrogen saturation3It is carried out in OH solution, scanning range is -0.8V~0.4V
(vs SCE), sweeping speed is 50mV/s, 20 circle of scanning.
Embodiment 8
(1) it takes 1.0g P123 to be dissolved in 30mL secondary distilled water and pours into round-bottomed flask and magnetic agitation, be passed through nitrogen
After 30min, 0.1g NaBH is taken4Be dissolved in 20mL secondary distilled water and directly pour into round-bottomed flask, immediately after to reaction solution with
20mL cobalt chloride (0.03mmol/L), gold chloride (0.03mmol/L) and potassium chloropalladate (0.03mmol/ is added dropwise in the speed of 3s/ drop
L mixed solution).Reaction temperature control stops reaction after reacting 6h, reaction solution is centrifugated, gained at room temperature (30 DEG C)
Product is with secondary distilled water centrifuge washing 3 times, then with dehydrated alcohol centrifuge washing 3 times to get catalyst for fuel cell.
(2) catalyst of synthesis is placed in vacuum drying oven drying, is ground to agate mortar powdered, be dispersed in
On porcelain boat and it is put into tube furnace and is heat-treated.It is vacuumized before heat treatment 3 times, N is passed through in heat treatment process2Gas shielded is adopted
Program fetch heating, heating rate are 3 DEG C/min, and heat treatment temperature is 200 DEG C, heat treatment time 2h.Then it naturally cools to
Room temperature is ground and is dispersed in ethanol to get the catalyst after heat treatment.
(3) catalyst after heat treatment is placed in the 0.5M H of 10mL2SO4In solution, ultrasonic agitation is uniformly mixed it,
Impregnate 6h.Then solution is centrifugated, with secondary distilled water centrifuge washing 3 times, disperse and be stored in dehydrated alcohol to get
Catalyst for fuel cell after heat treatment and removal alloying.
(4) catalytic performance of catalyst aoxidizes test characterization, the 1.0M that methanol oxidation test is saturated in nitrogen by methanol
It is carried out in NaOH solution, using cyclic voltammetry, scanning range is -0.9V~0.5V (vs SCE), and sweeping speed is 100mV/s,
20 circle of scanning；And the 1.0M NaOH+5.0M CH in nitrogen saturation3It is carried out in OH solution, scanning range is -0.8V~0.4V
(vs SCE), sweeping speed is 50mV/s, 20 circle of scanning.
Claims (10)
1. the preparation method of catalyst for fuel cell, which is characterized in that sequentially include the following steps:
(1) synthesis of catalyst: will be dissolved with P123 and CoCl2·6H2The mixed solution of O pours into round-bottomed flask, leads to N2And it is stirring
Under the conditions of mixing, NaBH is added dropwise4Aqueous solution is restored, to the NaBH in aqueous solution4After having hydrolyzed, K is added dropwise2PdCl4、HAuCl4·
3H2The mixed aqueous solution of O, the reaction was continued 4~12h after being added dropwise, reaction product is centrifuged, ultrasound is washed and ethyl alcohol is washed
After washing for several times, fuel cell CoAuPd catalyst is obtained；
(2) it the heat treatment of catalyst: is dispersed on porcelain boat after CoAuPd catalyst is dry, grinding and is put into tube furnace
In, it vacuumizes, leads to after inert gas natural cooling after being heat-treated 1~12h at 100~1000 DEG C, ethyl alcohol dispersion grinding obtains
The CoAuPd catalyst of heat treatment.
(3) removal alloying: by the CoAuPd catalyst soak after heat treatment in acid solution, ultrasound uses second distillation after impregnating
Water washing 3~5 times to get the CoAuPd catalyst after heat treatment and removal alloying.
2. the preparation method of catalyst for fuel cell described in claim 1, which is characterized in that the step (1) may be used also
Think P123 is soluble in water and is passed through N2, it is subsequently poured into NaBH4Aqueous solution, be added dropwise contain CoCl2·6H2O、K2PdCl4With
HAuCl4·3H2The mixed solution of O, the reaction was continued 4~12h after being added dropwise, reaction product is centrifuged, ultrasound is washed and
After ethanol washing 3~5 times, fuel cell CoAuPd catalyst can be obtained.
3. the preparation method of catalyst for fuel cell described in claim 1, which is characterized in that the step (3) may be used also
Think and applies the CoAuPd catalyst after heat treatment on the working electrode (s, using cyclic voltammetry, in 0.01~1.0M H2SO4It is molten
Carrying out cyclic voltammetry in liquid, scanning potential windows are -0.2V~0.9V, and sweeping speed is 1~1000mV/s, scanning circle number is 1~
100 circles are to get the CoAuPd catalyst after heat treatment and removal alloying.
4. the preparation method of the described in any item catalyst for fuel cell of claim 1-3, which is characterized in that P123 concentration is
1~1000mg/mL, sodium borohydride concentration are 0.1~50mg/mL, cobalt chloride concentration is 0.01~1mmol/L, gold chloride concentration
For 0.01~1mmol/L, potassium chloropalladate concentration is 0.01~1mmol/L, and the solution rate of addition is controlled in 1~10s/ drop,
Time for adding is controlled in 10~30min.
5. the preparation method of catalyst for fuel cell described in claim 1 or 4, which is characterized in that P123 concentration is 10mg/
ML, sodium borohydride concentration are 10mg/mL, cobalt chloride concentration 0.1mmol/L, gold chloride concentration are 0.03mmol/L, chlorine palladium acid
Potassium concn is 0.03mmol/L, and in 5s/ drop, time for adding is controlled in 30min for the solution rate of addition control.
6. the preparation method of catalyst for fuel cell described in claim 2 or 4, which is characterized in that P123 concentration is 10mg/
ML, sodium borohydride concentration are 10mg/mL, cobalt chloride concentration 0.03mmol/L, gold chloride concentration are 0.03mmol/L, chlorine palladium acid
Potassium concn is 0.03mmol/L, and in 5s/ drop, time for adding is controlled in 30min for the solution rate of addition control.
7. the preparation method of catalyst for fuel cell described in claim 1, which is characterized in that in the heat treatment process
Inert atmosphere is Ar or N2, programmed rate is 1~5 DEG C/min, and heat treatment temperature is 100~1000 DEG C, heat treatment time
For 1~12h.
8. the preparation method of catalyst for fuel cell described in claim 1, which is characterized in that in the heat treatment process
Inert atmosphere is Ar, and programmed rate is 2 DEG C/min, and heat treatment temperature is 300 DEG C, heat treatment time 2h.
9. the preparation method of catalyst for fuel cell described in claim 1 or 3, which is characterized in that during removal alloying,
Acid medium be mass fraction be 98% or more sulfuric acid, perchloric acid, one of hydrochloric acid or a variety of by any mass ratio
Combination；Preferably the acid medium is 0.1M H2SO4Solution, chemical removal alloying are 0.1M H2SO4It is impregnated in solution
Then 12h is used second distillation water washing 3 times；Electrochemistry removal alloying is 0.1M H2SO4Cyclic voltammetry scan in solution, potential
Window is -0.2V~0.9V, and sweeping speed is 100mV/s, and scanning circle number is 60 circles.
10. the catalyst that claim 1-9 either method is prepared catalysis oxidation methanol, ethyl alcohol, ethylene glycol, hydrogen reduction with
And the application on fuel cell.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810917566.9A CN109167078A (en) | 2018-08-13 | 2018-08-13 | The preparation method and applications of catalyst for fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810917566.9A CN109167078A (en) | 2018-08-13 | 2018-08-13 | The preparation method and applications of catalyst for fuel cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109167078A true CN109167078A (en) | 2019-01-08 |
Family
ID=64895768
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810917566.9A Pending CN109167078A (en) | 2018-08-13 | 2018-08-13 | The preparation method and applications of catalyst for fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109167078A (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008184671A (en) * | 2007-01-31 | 2008-08-14 | Tohoku Univ | Nano-porous metal and production method therefor |
| CN102335613A (en) * | 2011-07-12 | 2012-02-01 | 山东大学 | Graded-hole gold-copper alloy monolithic catalyst and preparation method thereof |
| CN102664275A (en) * | 2012-04-23 | 2012-09-12 | 北京化工大学 | Carbon-loaded kernel-shell copper-palladium-platinum catalyst for fuel battery and preparation method thereof |
| US20130224522A1 (en) * | 2010-10-26 | 2013-08-29 | W. L. Gore & Associates, Co., Ltd. | Anode-Side Catalyst Composition For Fuel Cells, and Membrane Electrode Assembly (MEA) For Solid Polymer Fuel Cells Which Comprises Same |
| CN103990468A (en) * | 2014-05-30 | 2014-08-20 | 中国科学院长春应用化学研究所 | Post-processing method for carbon-supported Pt-Fe catalyst |
| CN104588035A (en) * | 2015-01-20 | 2015-05-06 | 西南大学 | Preparation method for gold-palladium-cobalt core-shell structure (Au@PdCo)/carbon high-performance ethanol oxidation catalyst |
| CN106058277A (en) * | 2016-08-13 | 2016-10-26 | 三峡大学 | PdAu electrocatalyst for fuel cell and preparation method thereof |
| CN106179402A (en) * | 2016-07-21 | 2016-12-07 | 昆明理工大学 | A kind of preparation method of nanoporous palladium catalytic membrane |
| CN106910899A (en) * | 2017-02-27 | 2017-06-30 | 广西大学 | A kind of preparation method of N doping bivalve Rotating fields nanocatalyst |
-
2018
- 2018-08-13 CN CN201810917566.9A patent/CN109167078A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008184671A (en) * | 2007-01-31 | 2008-08-14 | Tohoku Univ | Nano-porous metal and production method therefor |
| US20130224522A1 (en) * | 2010-10-26 | 2013-08-29 | W. L. Gore & Associates, Co., Ltd. | Anode-Side Catalyst Composition For Fuel Cells, and Membrane Electrode Assembly (MEA) For Solid Polymer Fuel Cells Which Comprises Same |
| CN102335613A (en) * | 2011-07-12 | 2012-02-01 | 山东大学 | Graded-hole gold-copper alloy monolithic catalyst and preparation method thereof |
| CN102664275A (en) * | 2012-04-23 | 2012-09-12 | 北京化工大学 | Carbon-loaded kernel-shell copper-palladium-platinum catalyst for fuel battery and preparation method thereof |
| CN103990468A (en) * | 2014-05-30 | 2014-08-20 | 中国科学院长春应用化学研究所 | Post-processing method for carbon-supported Pt-Fe catalyst |
| CN104588035A (en) * | 2015-01-20 | 2015-05-06 | 西南大学 | Preparation method for gold-palladium-cobalt core-shell structure (Au@PdCo)/carbon high-performance ethanol oxidation catalyst |
| CN106179402A (en) * | 2016-07-21 | 2016-12-07 | 昆明理工大学 | A kind of preparation method of nanoporous palladium catalytic membrane |
| CN106058277A (en) * | 2016-08-13 | 2016-10-26 | 三峡大学 | PdAu electrocatalyst for fuel cell and preparation method thereof |
| CN106910899A (en) * | 2017-02-27 | 2017-06-30 | 广西大学 | A kind of preparation method of N doping bivalve Rotating fields nanocatalyst |
Non-Patent Citations (2)
| Title |
|---|
| LAI-MING LUO 等: ""Synthesis of 3D Thornbush-like Trimetallic CoAuPd Nanocatalysts and Electrochemical Dealloying for Methanol Oxidation and Oxygen Reduction Reaction"", 《ACS APPL. ENERGY MATER》 * |
| 周新文: ""CoPt和NiPt合金纳米催化剂：合成、自组装及其电催化和异常红外性能"", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111697239B (en) | Cobalt-iron alloy and nitrogen co-doped carbon oxygen reduction catalyst and preparation method and application thereof | |
| CN105854918B (en) | The composite material of nanometre grade cobalt basal granule and nitrogen-doped carbon, synthetic method and purposes | |
| CN108736031A (en) | A kind of self-supporting PtCo alloy nanoparticle catalyst and the preparation method and application thereof | |
| CN102088091A (en) | Carbon-carrying shell type copper-platinum catalyst for fuel cell and preparation method thereof | |
| CN105633425B (en) | A kind of Pdx@Pt/C nucleocapsid fuel battery cathod catalysts and preparation method thereof | |
| CN102101056B (en) | High-stability fuel-cell catalyst modified by oxide and preparation method thereof | |
| CN105810957B (en) | The preparation and application of a kind of platinum/nickel hydroxide cobalt hydroxide/graphene three-dimensional composite catalyst | |
| CN105107541A (en) | Preparing method for high-activity and high-stability composite catalyst for fuel cells | |
| CN106058277A (en) | PdAu electrocatalyst for fuel cell and preparation method thereof | |
| CN104368357B (en) | A kind of PdPtNi/C metal nano Catalysts and its preparation method and purposes | |
| CN103331172B (en) | Preparation method for non-Pt non-H anode catalyst of proton exchange membrane fuel cell (PEMFC) | |
| CN103586484B (en) | Pd-Ru alloy nano particle and its preparation and use | |
| CN103816894A (en) | Pt-Ru alloy nano electro-catalyst having doped graphene carrier and preparation method thereof | |
| CN108565476B (en) | Preparation method and application of ternary CoAuPd @ AuPd core-shell catalyst for fuel cell | |
| CN108155392A (en) | A kind of preparation method of redox graphene load Pd-M nano-composite catalysts | |
| CN111634954A (en) | Iron-modified cobalt-iron oxide with self-assembled flower ball structure and preparation and application thereof | |
| CN102784641A (en) | Preparation method of catalyst with high-activity palladium platinum core-shell structure | |
| CN103165914A (en) | Pt/Au/PdCo/C catalyst, and preparation and application thereof | |
| CN106207205A (en) | A kind of fuel cell PtPd eelctro-catalyst and preparation method thereof | |
| CN108746659B (en) | Flower-shaped AgPd nano alloy and preparation and use methods thereof | |
| CN105013483B (en) | Platinum palladium platinum/manganese dioxide/Graphene stratiform structure catalyst and preparation method | |
| CN108417848A (en) | A kind of platinum-nickel alloy catalyst nano material and the preparation method and application thereof having efficient electric catalytic oxidation-reduction performance | |
| CN110931804B (en) | CeO carried by Pt-Ni-Cu ternary alloy2Preparation of composite material and research on formic acid catalytic performance of composite material | |
| CN109786773B (en) | PtPdCu ternary alloy catalyst and preparation method and application thereof | |
| CN109873174A (en) | A kind of low-temperature fuel cell supports the preparation method of platinum Pd-Co alloy structure catalyst with three-dimensional carrier |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190108 |
|
| RJ01 | Rejection of invention patent application after publication |