CN108933265A - A kind of alloy nano cage catalyst and its preparation method and application - Google Patents
A kind of alloy nano cage catalyst and its preparation method and application Download PDFInfo
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- CN108933265A CN108933265A CN201811085177.0A CN201811085177A CN108933265A CN 108933265 A CN108933265 A CN 108933265A CN 201811085177 A CN201811085177 A CN 201811085177A CN 108933265 A CN108933265 A CN 108933265A
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Abstract
The present invention provides a kind of alloy nano cage catalyst and its preparation method and application, the catalyst includes noble metal and non-noble metal alloy；The catalyst is in flower-shaped hollow Nano basket structure.Catalyst of the present invention replaces noble metal to form alloy with base metal part, has synergistic effect, electronic structure optimization, catalyst stability enhancing between the two；There is the catalyst octahedra horn craving to lose hollow structure, stable structure, large specific surface area, meanwhile, noble metal usage amount is few, and catalyst is at low cost；The catalyst is applied to direct methanol fuel cell, can achieve 800A/g or more to the catalytic activity of methanol oxidation.
Description
Technical field
The invention belongs to catalyst technical field, it is related to a kind of alloy nano cage catalyst and its preparation method and application.
Background technique
Energy problem is one of significant problem of today's society, with the worsening shortages of fossil energy, develops renewable energy
The effective use of the energy is realized in source, is problem in the urgent need to address.Fuel cell utilizes skill as a kind of new high efficiency of energy
Art, simultaneously because having many advantages, such as light, energy density is high, also can be used as important energy storage material.Methanol is a kind of cleaning energy
Source, and be renewable energy, it is usually applied to fuel cell field.Direct methanol fuel cell is due to energy density height, the energy
High conversion rate, operation system are simple etc., have obtained extensive concern.Two kinds are primarily present in direct methanol fuel cell instead
It answers, i.e. oxygen reduction reaction and methanol oxidation, wherein methanol oxidation decides the efficiency of entire fuel cell.Therefore,
Research preparation there is the catalyst of high catalytic performance to be of great significance methanol oxidation.
Currently, the existing many researchs of fuel-cell catalyst, most of effective catalysts are mainly nonetheless focused upon noble metal
On, however the earth reserves of noble metal are extremely low, expensive, cost is too high, and CO poisoning easily occurs and influences its catalytic performance,
Such as the catalyst such as platinum carbon, palladium carbon in the market, expensive, nano particle is easy to reunite, and stability is very poor, can not push away always
Dynamic fuel cell realizes commercialization.Therefore, the catalyst for preparing high efficiency low cost is still very big challenge.
Aiming at the problem that existing catalyst, Many researchers also make improvement from raw material, structure and pattern etc..CN
103007964 A disclose a kind of preparation method of direct methanol fuel cell charcoal load hollow Nano gold nickel alloy catalyst,
This method includes preparing the golden nickel of charcoal load with the precursor compound of ethylene glycol coreduction metallic gold and nickel under alkaline system to answer
Nanoparticle is closed, is heat-treated under the conditions of 400~600 DEG C in nitrogen atmosphere later, realizes the alloying of metallic nickel and gold,
Then washing is impregnated to remove extra non-alloyed metal (AM) nickel in dilute sulfuric acid.Although the catalyst is by golden nickel alloy group
At, but monolith design does not improve, and hollow structural part also is difficult to, be unfavorable for electronic structure optimization and
The raising of methanol oxidation catalytic property.108003355 A of CN discloses a kind of one pot of coreduction solvent structure hollow cubic
The synthetic method of PtCu nanometers of frame materials of body by by metal precursor acetylacetone,2,4-pentanedione platinum and copper chloride, then is aided with regulatory molecule
PtCu nanometers of frame materials are prepared in hexadecyltrimethylammonium chloride, reducing agent ethanol amine and solvent oleyl amine, solvothermal
Material, but the catalyst is mainly used for the reduction reaction of glycerine and oxygen, and requirement of this method to reaction condition is more stringent,
The formation of hollow cube is more difficult.
In conclusion the improvement of catalyst for fuel cell, needs to consider various factors, from pattern, structure and group
At etc. set about, while simplify preparation process, reduce cost.
Summary of the invention
In view of the problems of the existing technology, the purpose of the present invention is to provide a kind of alloy nano cage catalyst and its systems
Preparation Method and purposes replace noble metal with base metal part in the alloy catalyst, regulate and control electronic structure, have between the two
There is synergistic effect, improves the stability of catalyst；The nanocages catalyst is hollow structure, and specific surface area is larger, active sites
Point is more, and mass transfer distance is shorter, and the above corrective measure can effectively improve the catalytic activity of the catalyst；Meanwhile the side
Method simple process, short preparation period have a extensive future.
To achieve this purpose, the present invention adopts the following technical scheme:
In a first aspect, the present invention provides a kind of alloy nano cage catalyst, the catalyst includes noble metal and non-expensive
The alloy of metal；The catalyst is in flower-shaped hollow Nano basket structure.
In the present invention, the alloy nano cage catalyst improves existing catalyst in terms of the Nomenclature Composition and Structure of Complexes two,
By replacing noble metal with base metal part, reduce the dosage of noble metal, and there is synergistic effect, Ke Yijia between the two
The transmitting of fast electronics improves its stability and electrocatalysis characteristic, and the catalyst is in hollow Nano basket structure, have density low and
The characteristics of large specific surface area, reduces the cost of catalyst, shortens mass transfer distance, improves catalytic efficiency.
It is used as currently preferred technical solution below, but not as the limitation of technical solution provided by the invention, passes through
Following technical scheme can preferably reach and realize technical purpose and beneficial effect of the invention.
As currently preferred technical solution, the noble metal includes any one in palladium, ruthenium, platinum or gold or at least two
The combination of kind, the combination is typical but non-limiting example has: the combination of the combination of palladium and ruthenium, ruthenium and platinum, the group of palladium, platinum and gold
Conjunction etc., preferably palladium.
Preferably, the base metal includes copper.
Preferably, in the catalyst non-noble metal mass fraction be 10~25wt%, such as 10wt%, 12wt%,
15wt%, 18wt%, 20wt%, 22wt% or 25wt% etc., it is not limited to cited numerical value, in the numberical range its
His unlisted numerical value is equally applicable.
As currently preferred technical solution, the catalyst is in that octahedra horn craving loses hollow structure.
Preferably, the partial size of the catalyst is 400~500nm, such as 400nm, 420nm, 440nm, 460nm, 480nm
Or 500nm etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable.
Preferably, the wall thickness of the catalyst be 5~20nm, such as 5nm, 8nm, 10nm, 12nm, 15nm, 18nm or
20nm etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable.
Preferably, the specific surface area of the catalyst is 40~60m2/ g, such as 40m2/g、42m2/g、45m2/g、48m2/
g、50m2/g、54m2/g、57m2/ g or 60m2/ g etc., it is not limited to cited numerical value, interior other of the numberical range are not arranged
The numerical value of act is equally applicable.
In the present invention, the structure and partial size of the catalyst are mainly determined by template used dose of base metal presoma
, catalyst particle size is too big, then its specific surface area is smaller, is also unfavorable for the stability of hollow structure；Catalyst particle size is too small,
The control of appearance structure is more difficult in preparation process.
Second aspect, the present invention provides a kind of preparation method of above-mentioned alloy nano cage catalyst, the method includes
Following steps:
(1) cuprous oxide dispersion liquid is mixed with noble metal precursor body, reacts, obtains alloy product；
(2) unreacted cuprous oxide in alloy product that step (1) obtains is performed etching, obtains alloy nano cage and urges
Agent.
In the present invention, using cuprous oxide as template, redox reaction occurs with noble metal precursor body, while also aerobic
Change itself cuprous disproportionated reaction, obtains the alloy of copper and noble metal, then remove removing template with etching agent, obtain alloy nano cage and urge
Agent.
As currently preferred technical solution, step (1) cuprous oxide is in octahedra horn craving arbor.
Preferably, the partial size of step (1) described cuprous oxide be 400~500nm, such as 400nm, 420nm, 440nm,
460nm, 480nm or 500nm etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are same
Sample is applicable in.
Preferably, step (1) described cuprous oxide preparation method the following steps are included:
(a) mixed liquor including mantoquita, sodium potassium tartrate tetrahydrate and alkali is prepared；
(b) palladium chloride and glucose are added into the mixed liquor that step (a) obtains, reacts, obtains cuprous oxide.
In the present invention, when preparing cuprous oxide, alkaline cupric tartrate test solution is configured first, by by mantoquita, potassium tartrate
It is formed after sodium and alkali soluble solution, palladium chloride and glucose is then added, glucose, will as catalyst as reducing agent, palladium chloride
Cupric tartrate complex is reduced to cuprous oxide, and the micro amount of oxygen in solution is under the action of palladium by the slow oxygen of cuprous oxide later
Change, and realize the selective etch of cuprous oxide, obtains the cuprous oxide with horn craving arbor.
As currently preferred technical solution, step (a) mantoquita includes appointing in copper sulphate, copper chloride or copper acetate
It anticipates a kind of or at least two combinations, the combination typical case but non-limiting example has: the combination of copper sulphate and copper chloride, chlorination
The combination of copper and copper acetate, copper sulphate, copper chloride and combination of copper acetate etc..
Preferably, step (a) alkali includes potassium hydroxide and/or sodium hydroxide.
Preferably, the mass ratio of step (a) mantoquita and step (b) palladium chloride is (50~175): 1, such as
50:1,60:1,80:1,100:1,120:1,140:1,160:1 or 175:1 etc., it is not limited to cited numerical value, the number
It is equally applicable to be worth other unlisted numerical value in range.
Preferably, the mass ratio of step (a) mantoquita and step (b) glucose is (0.6~0.9): 1, such as
0.6:1,0.65:1,0.7:1,0.75:1,0.8:1,0.85:1 or 0.9:1 etc., it is not limited to cited numerical value, the number
It is equally applicable to be worth other unlisted numerical value in range.
Preferably, step (b) reaction carries out under water bath condition.
Preferably, the bath temperature is 50~80 DEG C, such as 50 DEG C, 55 DEG C, 60 DEG C, 65 DEG C, 70 DEG C, 75 DEG C or 80 DEG C
Deng, it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable, preferably 65~75
℃。
Preferably, the water bath time be 2~4h, such as 2h, 2.25h, 2.5h, 2.75h, 3h, 3.25h, 3.5h,
3.75h or 4h etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable, excellent
It is selected as 2~3h.
As currently preferred technical solution, step (1) the noble metal precursor body includes noble metal acid and/or your gold
Belong to salt.
Preferably, step (1) the noble metal precursor body includes palladium presoma, ruthenium presoma, platinum presoma or golden forerunner
Any one in body or at least two combination, the combination is typical but non-limiting example has: palladium presoma and ruthenium presoma
Combination, the combination of palladium presoma and platinum presoma, the combination of platinum presoma and golden presoma, palladium presoma, ruthenium presoma and
The combination etc. of platinum presoma, preferably palladium presoma.
Preferably, the palladium presoma includes any one in chlorine palladium acid sodium, potassium chloropalladate or chlorine palladium acid or at least two
Combination, the combination is typical but non-limiting example has: the combination of chlorine palladium acid sodium and potassium chloropalladate, potassium chloropalladate and chlorine palladium acid
Combination, chlorine palladium acid sodium, potassium chloropalladate and combination of chlorine palladium acid etc..
Preferably, the concentration of step (1) the noble metal precursor body is 5~20mmol/L, such as 5mmol/L, 8mmol/
L, 10mmol/L, 12mmol/L, 15mmol/L, 18mmol/L or 20mmol/L etc., it is not limited to cited numerical value, it should
Other unlisted numerical value are equally applicable in numberical range, preferably 10mmol/L.
Preferably, the molar ratio of step (1) cuprous oxide and noble metal precursor body is (0.52~3.5): 1, such as
0.52:1,1:1,1.5:1,2:1,2.5:1,3:1 or 3.5:1 etc., it is not limited to cited numerical value, in the numberical range
Other unlisted numerical value are equally applicable.
It preferably, further include surfactant in step (1) described dispersion liquid.
Preferably, the surfactant includes polyvinylpyrrolidone and/or lauryl sodium sulfate.
Preferably, the mass ratio of the surfactant and step (1) described cuprous nano frame is (5~10): 1,
Such as 5:1,6:1,7:1,8:1,9:1 or 10:1 etc., it is not limited to cited numerical value, interior other of the numberical range are not arranged
The numerical value of act is equally applicable.
In the present invention, the addition of surfactant can control reaction rate, reduce the rate of redox reaction, simultaneously
Disproportionated reaction occurs, forms alloy；And metal ion can also be strapped in cuprous oxide surface by surfactant, be conducive to alloy
Product maintains original structure.
As currently preferred technical solution, the temperature of step (1) described reaction is 20~40 DEG C, such as 20 DEG C, 22
DEG C, 25 DEG C, 27 DEG C, 30 DEG C, 32 DEG C, 35 DEG C, 38 DEG C or 40 DEG C etc., it is not limited to cited numerical value, the numberical range
Other interior unlisted numerical value are equally applicable.
Preferably, the time of step (1) described reaction be 15~60min, such as 15min, 20min, 25min, 30min,
35min, 40min, 45min, 50min, 55min or 60min etc., it is not limited to cited numerical value, in the numberical range
Other unlisted numerical value are equally applicable.
Preferably, step (1) reaction carries out under agitation.
In the present invention, cuprous oxide and noble metal precursor precursor reactant restore precious metal simple substance, and cuprous oxide is sent out
Raw disproportionated reaction, can be generated copper, and the two carries out simultaneously, generate the alloy of noble metal and copper.
Preferably, step (1) is described after reaction, through filtering, carrying out washing treatment, obtains alloy product.
As currently preferred technical solution, it includes ammonium hydroxide that step (2), which etches etching agent used,.
Preferably, the mass fraction of the ammonium hydroxide be 25~28wt%, such as 25wt%, 25.5wt%, 26wt%,
26.5wt%, 27wt%, 27.5wt% or 28wt% etc., it is not limited to cited numerical value, in the numberical range other
Unlisted numerical value is equally applicable.
In the present invention, the addition of etching agent is excessive, allows and reacts remaining cuprous oxide and etched completely, is formed empty
Core structure.
Preferably, the time of the etching is 8~15h, for example, 8h, 9h, 10h, 11h, 12h, 13h, 14h or 15h etc.,
It is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable.
Preferably, after the etching, etch product is washed, it is dry, obtain alloy nano cage catalyst.
The third aspect, the present invention provides the purposes of above-mentioned alloy nano cage catalyst, the catalyst is used as fuel electricity
Pond catalyst.
Preferably, the catalyst is used as direct methanol fuel cell catalyst.
Compared with prior art, the invention has the following advantages:
(1) catalyst of the present invention replaces noble metal to form alloy with base metal part, has collaboration between the two
Effect, electronic structure optimization, catalyst stability are strong；
(2) catalyst of the present invention has flower-shaped hollow Nano basket structure, and large specific surface area, electro-active site is more, together
When preparation method it is simple, generate the period it is short；
(3) catalyst noble metal usage amount of the present invention is reduced, and cost reduces, to the catalytic activity of methanol oxidation
It can achieve 800A/g or more.
Detailed description of the invention
Fig. 1 is palladium nanocages catalyst described in alloy nano cage catalyst, comparative example 1 described in the embodiment of the present invention 4 and right
The cyclic voltammetry curve figure of business palladium carbon nanocatalyst described in ratio 2.
Specific embodiment
In order to better illustrate the present invention, it is easy to understand technical solution of the present invention, below further specifically to the present invention
It is bright.But following embodiments is only simple example of the invention, does not represent or limit the scope of the present invention, this
Invention protection scope is subject to claims.
Specific embodiment of the invention part provides a kind of alloy nano cage catalyst and preparation method thereof, the catalysis
Agent includes noble metal and non-noble metal alloy；The catalyst is in flower-shaped hollow Nano basket structure.
Preparation method includes the following steps:
(1) cuprous oxide dispersion liquid is mixed with noble metal precursor body, reacts, obtains alloy product；
(2) unreacted cuprous oxide in alloy product that step (1) obtains is performed etching, obtains alloy nano cage and urges
Agent.
The following are typical but non-limiting embodiments of the invention:
Embodiment 1:
The preparation method for present embodiments providing a kind of cuprous oxide, the described method comprises the following steps:
(1) 0.35g copper sulphate, 1.25g sodium potassium tartrate tetrahydrate and 0.225g potassium hydroxide are separately added into water, are mixed
Liquid；
(2) 4.8mg palladium chloride and 0.450g glucose are added into the mixed liquor that step (a) obtains, stirs evenly, 75
Water-bath 2.5h under the conditions of DEG C obtains the cuprous oxide with horn craving arbor after centrifuge washing is dry.
Embodiment 2:
The preparation method for present embodiments providing a kind of cuprous oxide, the described method comprises the following steps:
(1) 0.30g copper chloride, 1.25g sodium potassium tartrate tetrahydrate and 0.161g sodium hydroxide are separately added into water, are mixed
Liquid；
(2) 6.0mg palladium chloride and 0.5g glucose are added into the mixed liquor that step (a) obtains, stirs evenly, at 50 DEG C
Under the conditions of water-bath 4h obtain the cuprous oxide with horn craving arbor after centrifuge washing is dry.
Embodiment 3:
The preparation method for present embodiments providing a kind of cuprous oxide, the described method comprises the following steps:
(1) 0.40g copper acetate, 1.25g sodium potassium tartrate tetrahydrate and 0.225g potassium hydroxide are separately added into water, are mixed
Liquid；
(2) 2.3mg palladium chloride and 0.444g glucose are added into the mixed liquor that step (a) obtains, stirs evenly, 80
Water-bath 2h under the conditions of DEG C obtains the cuprous oxide with horn craving arbor after centrifuge washing is dry.
Embodiment 4:
A kind of alloy nano cage catalyst and preparation method thereof is present embodiments provided, the catalyst includes that palladium copper closes
Gold, wherein the mass fraction of copper is 16wt%；
The catalyst is in that octahedra horn craving loses hollow Nano basket structure, partial size 450nm, wall thickness 15nm.
The preparation method of the catalyst the following steps are included:
(1) 50mg polyvinylpyrrolidone is added after being dispersed in water the cuprous oxide 7.2mg that embodiment 1 obtains, stirs
After mixing uniformly, the chlorine palladium acid that 5mL concentration is 10mmol/L is added, reacts, the reaction temperature is 30 DEG C, and the reaction time is
20min obtains palladium-copper alloy through filtering, carrying out washing treatment；
(2) palladium-copper alloy that step (1) obtains is placed in the ammonium hydroxide that 7mL mass concentration is 27wt%, etching removal is not
The cuprous oxide of reaction, etch period 10h, washs etch product, dry, obtains the catalysis of palladium-copper alloy nanocages
Agent.
It disperses the palladium-copper alloy nanocages catalyst being prepared in dehydrated alcohol with the concentration of 4mg/mL, takes 14 μ L
10 μ L 0.1%nafion solution are added dropwise in the glass-carbon electrode handled well, after drying again for drop, after drying, using it as working electrode,
Platinum plate electrode is to electrode, and Ag/AgCl is reference electrode, is electricity with the methanol of the potassium hydroxide solution of 0.5mol/L and 1mol/L
Liquid is solved, its catalytic performance to methanol oxidation, cyclic voltammetry curve such as Fig. 1 institute are tested with the scanning speed of 50mV/s
Show.
In the present embodiment, as shown in Figure 1, the catalyst is urged for the methanol oxidation in direct methanol fuel cell
Change activity is indicated with current density, can achieve 821.5A/g.
Embodiment 5:
A kind of alloy nano cage catalyst and preparation method thereof is present embodiments provided, the catalyst includes that platinoid closes
Gold, wherein the mass fraction of copper is 10wt%；
The catalyst is in that octahedra horn craving loses hollow Nano basket structure, partial size 400nm, wall thickness 20nm.
The preparation method of the catalyst the following steps are included:
(1) 36mg lauryl sodium sulfate is added after being dispersed in water the cuprous oxide 7.2mg that embodiment 2 obtains, stirs
After mixing uniformly, the platinic sodium chloride that 4.8mL concentration is 20mmol/L is added, reacts, the reaction temperature is 20 DEG C, when reaction
Between be 40min, through filtering, carrying out washing treatment, obtain Mock gold；
(2) Mock gold that step (1) obtains is placed in the ammonium hydroxide that 5mL mass concentration is 25wt%, etching removal is not
The cuprous oxide of reaction, etch period 8h, washs etch product, dry, obtains Mock gold nanocages catalyst.
The Mock gold nanocages catalyst being prepared is used for the oxidation of the methanol in direct methanol fuel cell, test
Its catalytic performance, the test condition is referring to embodiment 4.
In the present embodiment, the catalyst is used for fuel cell methanol oxidation, and catalytic activity can achieve
807.4A/g。
Embodiment 6:
A kind of alloy nano cage catalyst and preparation method thereof is present embodiments provided, the catalyst includes Jin Tonghe
Gold, wherein the mass fraction of copper is 25wt%；
The catalyst is in that octahedra horn craving loses hollow Nano basket structure, partial size 500nm, wall thickness 5nm.
The preparation method of the catalyst the following steps are included:
(1) 72mg polyvinylpyrrolidone is added after being dispersed in water the cuprous oxide 7.2mg that embodiment 3 obtains, stirs
After mixing uniformly, the potassium chloroaurate that 2.9mL concentration is 5mmol/L is added, reacts, the reaction temperature is 40 DEG C, when reaction
Between be 15min, through filtering, carrying out washing treatment, obtain gold copper；
(2) gold copper that step (1) obtains is placed in the ammonium hydroxide that 10mL mass concentration is 28wt%, etching removal is not
The cuprous oxide of reaction, etch period 15h, washs etch product, dry, obtains the catalysis of gold copper nanocages
Agent.
The gold copper nanocages catalyst being prepared is used for the oxidation of the methanol in direct methanol fuel cell, test
Its catalytic performance, the test condition is referring to embodiment 4.
In the present embodiment, the catalyst is used for fuel cell methanol oxidation, and catalytic activity can achieve
803.6A/g。
Embodiment 7:
A kind of alloy nano cage catalyst and preparation method thereof is present embodiments provided, the catalyst includes that palladium ruthenium copper closes
Gold, wherein the mass fraction of copper is 20wt%；
The catalyst is in that octahedra horn craving loses hollow Nano basket structure, partial size 480nm, wall thickness 10nm.
The preparation method of the catalyst the following steps are included:
(1) 57.6mg lauryl sodium sulfate is added after being dispersed in water the cuprous oxide 7.2mg that embodiment 1 obtains,
After mixing evenly, 2.5mL concentration is added is the chlorine palladium acid of 10mmol/L and the mixed liquor of ruthenium hydrochloride, is reacted, described anti-
Answering temperature is 30 DEG C, reaction time 20min, through filtering, carrying out washing treatment, obtains palladium ruthenium copper alloy；
(2) the palladium ruthenium copper alloy that step (1) obtains is placed in the ammonium hydroxide that 7.5mL mass concentration is 26wt%, etching is gone
Except unreacted cuprous oxide, etch period 12h washs etch product, dry, obtains palladium ruthenium copper alloy nanocages
Catalyst.
The palladium ruthenium copper alloy nanocages catalyst being prepared is used for the oxidation of the methanol in direct methanol fuel cell, is surveyed
Its catalytic performance is tried, the test condition is referring to embodiment 4.
In the present embodiment, the catalyst is used for fuel cell methanol oxidation, and catalytic activity can achieve
812.0A/g。
Embodiment 8:
A kind of preparation method of alloy nano cage catalyst is present embodiments provided, the method is referring in embodiment 4
Method, difference are only that: step is added without polyvinylpyrrolidone in (2).
The palladium-copper alloy nanocages catalyst being prepared is used for the oxidation of the methanol in direct methanol fuel cell, test
Its catalytic performance, the test condition is referring to embodiment 4.
In the present embodiment, due to not having addition surfactant, the reaction rate of cuprous oxide and noble metal acid is very fast, because
This disproportionated reaction rate is slower, or even is difficult to happen, and copper content is extremely low in the product of generation, and nanocages structural stability is poor,
It acts synergistically between metal unobvious, is used for fuel cell methanol oxidation, catalytic activity is only 620.0A/g.
Comparative example 1:
This comparative example provides a kind of palladium nanoparticle catalyst and preparation method thereof, the structure and implementation of the catalyst
Example 4 is identical, is only made of precious metal palladium on composition.
The method is only that referring to the method in embodiment 4, difference: it is 10mmol/ that 12mL concentration is added in step (1)
The chlorine palladium acid of L.
The palladium nanocages catalyst being prepared is used for the oxidation of the methanol in direct methanol fuel cell, tests its catalysis
Performance, as shown in Figure 1, the test condition is referring to embodiment 4.
In this comparative example, the catalyst is only made of noble metal, and the cost is relatively high, compared with Example 4, single
The electronic structure of metal is not optimized, and without the synergistic effect between alloy, as shown in Figure 1, is used for fuel cell
Methanol oxidation, catalytic activity indicate with current density, only 607.5A/g.
Comparative example 2:
This comparative example provides a kind of business palladium carbon nanocatalyst.
The palladium carbon nanocatalyst is used for the oxidation of the methanol in direct methanol fuel cell, tests its catalytic performance,
As shown in Figure 1, the test condition is referring to embodiment 4.
In this comparative example, the palladium-carbon catalyst higher cost, nano particle is easy to reunite, and stability is poor, and compares table
Area is less than catalyst described in the embodiment of the present invention, as shown in Figure 1, is used for fuel cell methanol oxidation, catalysis is lived
Property indicates with current density, only 306.4A/g.
It can be seen that catalyst of the present invention with comparative example based on the above embodiments and your gold replaced with base metal part
Category forms alloy, and electronic structure is optimized between the two, has synergistic effect, also improves the stability of catalyst；It is described to urge
The composition of alloy and hollow structure of agent, significantly reduce the usage amount of noble metal, reduce catalyst cost, and compare table
Area is larger, and mass transfer distance is shorter；When the above improvement effectively increases the catalyst for direct methanol fuel cell
Catalytic activity, catalytic activity can achieve 800A/g or more.
Applicant's statement, the present invention illustrates detailed applications method of the invention by examples detailed above, but the present invention is not
Be confined to above-mentioned detailed applications method, that is, do not mean that the invention must rely on the above detailed methods to implement.The technology
The technical staff in field it will be clearly understood that any improvement in the present invention, equivalent transformation and helper component to raw material of the present invention
Addition, actual conditions and selection of mode etc., all of which fall within the scope of protection and disclosure of the present invention.
Claims (10)
1. a kind of alloy nano cage catalyst, which is characterized in that the catalyst includes noble metal and non-noble metal alloy；Institute
Catalyst is stated in flower-shaped hollow Nano basket structure.
2. alloy nano cage catalyst according to claim 1, which is characterized in that the noble metal include palladium, ruthenium, platinum or
Any one in gold or at least two combination, preferably palladium；
Preferably, the base metal includes copper；
Preferably, non-noble metal mass fraction is 10~25wt% in the catalyst.
3. catalyst according to claim 1 or 2, which is characterized in that preferably, the catalyst is in octahedra horn craving erosion
Hollow structure；
Preferably, the partial size of the catalyst is 400~500nm；
Preferably, the wall thickness of the catalyst is 5~20nm；
Preferably, the specific surface area of the catalyst is 40~60m2/g。
4. a kind of preparation method of catalyst as described in any one of claims 1-3, which is characterized in that the method includes with
Lower step:
(1) cuprous oxide dispersion liquid is mixed with noble metal precursor body, reacts, obtains alloy product；
(2) unreacted cuprous oxide in alloy product that step (1) obtains is performed etching, obtains the catalysis of alloy nano cage
Agent.
5. the preparation method according to claim 4, which is characterized in that step (1) cuprous oxide is in octahedra horn craving
Arbor；
Preferably, the partial size of step (1) described cuprous oxide is 400~500nm；
Preferably, step (1) described cuprous oxide preparation method the following steps are included:
(a) mixed liquor including mantoquita, sodium potassium tartrate tetrahydrate and alkali is prepared；
(b) palladium chloride and glucose are added into the mixed liquor that step (a) obtains, reacts, obtains cuprous oxide.
6. preparation method according to claim 5, which is characterized in that step (a) mantoquita includes copper sulphate, copper chloride
Any one in copper acetate or at least two combination；
Preferably, step (a) alkali includes potassium hydroxide and/or sodium hydroxide；
Preferably, the mass ratio of step (a) mantoquita and step (b) palladium chloride is (50~175): 1；
Preferably, the mass ratio of step (a) mantoquita and step (b) glucose is (0.6~0.9): 1；
Preferably, step (b) reaction carries out under water bath condition；
Preferably, the bath temperature is 50~80 DEG C, preferably 65~75 DEG C；
Preferably, the water bath time is 2~4h, preferably 2~3h.
7. according to the described in any item preparation methods of claim 4-6, which is characterized in that step (1) the noble metal precursor body
Including noble metal acid and/or precious metal salt；
Preferably, step (1) the noble metal precursor body includes in palladium presoma, ruthenium presoma, platinum presoma or golden presoma
Any one or at least two combination, preferably palladium presoma；
Preferably, the palladium presoma includes the group of any one in chlorine palladium acid, chlorine palladium acid sodium or potassium chloropalladate or at least two
It closes；
Preferably, the concentration of step (1) the noble metal precursor body is 5~20mmol/L, preferably 10mmol/L；
Preferably, the molar ratio of step (1) cuprous oxide and noble metal precursor body is (0.52~3.5): 1；
It preferably, further include surfactant in step (1) described dispersion liquid；
Preferably, the surfactant includes polyvinylpyrrolidone and/or lauryl sodium sulfate；
Preferably, the mass ratio of the surfactant and step (1) described cuprous oxide is (5~10): 1.
8. according to the described in any item preparation methods of claim 4-7, which is characterized in that the temperature of step (1) described reaction is
20~40 DEG C；
Preferably, the time of step (1) described reaction is 15~40min；
Preferably, step (1) reaction carries out under agitation；
Preferably, step (1) is described after reaction, through filtering, carrying out washing treatment, obtains alloy product.
9. according to the described in any item preparation methods of claim 4-8, which is characterized in that step (2) etches etching agent packet used
Include ammonium hydroxide；
Preferably, the mass fraction of the ammonium hydroxide is 25~28wt%；
Preferably, the time of the etching is 8~15h；
Preferably, after the etching, etch product is washed, it is dry, obtain alloy nano cage catalyst.
10. a kind of purposes of catalyst as described in any one of claims 1-3, which is characterized in that the catalyst is used as combustion
Expect cell catalyst；
Preferably, the catalyst is used as direct methanol fuel cell catalyst.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110241438A (en) * | 2018-03-08 | 2019-09-17 | 天津大学 | Foam copper supports palladium-copper alloy nanocages catalyst and preparation method thereof |
| CN111987328A (en) * | 2020-08-17 | 2020-11-24 | 河南师范大学 | Preparation method of electrocatalyst with nanoparticle structure for methanol fuel cell |
| CN113258085A (en) * | 2021-04-19 | 2021-08-13 | 湖南大学 | Oxygen-containing silicon nanosheet supported noble metal catalyst and preparation method and application thereof |
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| CN108520965A (en) * | 2018-04-04 | 2018-09-11 | 陕西师范大学 | A kind of preparation method of platinum-noble metal-copper ternary alloy nano hollow cube |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110241438A (en) * | 2018-03-08 | 2019-09-17 | 天津大学 | Foam copper supports palladium-copper alloy nanocages catalyst and preparation method thereof |
| CN111987328A (en) * | 2020-08-17 | 2020-11-24 | 河南师范大学 | Preparation method of electrocatalyst with nanoparticle structure for methanol fuel cell |
| CN113258085A (en) * | 2021-04-19 | 2021-08-13 | 湖南大学 | Oxygen-containing silicon nanosheet supported noble metal catalyst and preparation method and application thereof |
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