CN108682876A - A kind of high activity has the cube nano Pd catalyst and preparation method thereof of meso-hole structure - Google Patents
A kind of high activity has the cube nano Pd catalyst and preparation method thereof of meso-hole structure Download PDFInfo
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Abstract
A kind of high activity has the cube nano Pd catalyst and preparation method thereof of meso-hole structure, it belongs to the preparation field of efficient palladium nanocatalyst.The present invention is using 3- methyl-hexadecyl imidazoles as protective agent; ascorbic acid is reducing agent; after evenly mixing by palladium salt precursor solution and HMIB solution, AA solution reduction certain times are added at a certain temperature, the cube nano Pd catalyst with meso-hole structure is made.Compared with palladium nanoparticle catalyst prepared by conventional method, palladium nanocatalyst produced by the present invention has cube pattern, is uniformly dispersed, and there are meso-hole structures for inside, have more active sites, to show higher electro catalytic activity.
Description
Technical field
The invention belongs to the preparation fields of efficient palladium nanocatalyst, and in particular to a kind of high activity has meso-hole structure
Cube nano Pd catalyst and preparation method thereof.
Background technology
In face of the energy and environmental crisis of current getting worse, fuel cell is played in the exploitation of the energy and conversion field
Vital effect.Wherein, direct methanol fuel cell (DMFC) is received due to its apparent energy density per unit volume advantage
Extensive concern.Platinum nano catalyst is most common efficient, stable, durable DMFC catalyst, but it is expensive.Therefore,
It develops and is of great significance with high catalytic activity, high stability and catalyst cheap and easy to get.Palladium is as platinum metal
With similar chemical property, but electro catalytic activity is poor, is participated in by improving the surface texture of palladium nano-particles to change
The absorption of reaction molecular and activation process, and then improve its electrocatalysis characteristic great potential.But current palladium nanocatalyst is most
For spheric granules, activity is relatively low in methanol oxidation, and the palladium nanocatalyst with specific surface structure is prepared mostly
Process is complex.
Invention content
The object of the present invention is to provide cube nano Pd catalyst and its preparations that a kind of high activity has meso-hole structure
Method.
The invention is realized by the following technical scheme：
A kind of preparation method of cube nano Pd catalyst of the high activity with meso-hole structure, includes the following steps：
Palladium salt, 3- methyl-hexadecyl imidazoles, ascorbic acid are dissolved in deionized water by step 1 respectively, configuration
At palladium salt precursor solution, 3- methyl-hexadecyl imidazole solution, ascorbic acid solution, for use；
Step 2, the palladium salt precursor solution that step 1 has been configured and 3- methyl-hexadecyl imidazole solution are added
To 5~15min is stirred in deionized water, ascorbic acid solution is added, controlling reaction temperature is 40~70 DEG C under stirring condition,
0.5~4h of reaction time, the palladium salt precursor solution, 3- methyl-hexadecyl imidazole solution, ascorbic acid solution
Volume ratio with deionized water is 2~8：0.05~0.5：1~4：27.5~56.95, the solution for later use after reaction；
Solution after step 2 reaction is carried out centrifugal treating by step 3, is removed supernatant, is washed with deionized 3~5 times
Gained sediment, by the sediment ultrasonic disperse after washing in absolute ethyl alcohol, the high activity for being made described has meso-hole structure
Cube nano Pd catalyst.
A kind of high activity of the present invention has the preparation method of the cube nano Pd catalyst of meso-hole structure, step
Palladium salt described in 1 is Na2PdCl4、K2PdCl4、H2PdCl4、Pd(NO3)2In any one.
A kind of high activity of the present invention has the preparation method of the cube nano Pd catalyst of meso-hole structure, step
A concentration of 0.1mol/ of a concentration of 0.01mol/L, 3- methyl-hexadecyl imidazole solution of palladium salt precursor solution in 1
L, a concentration of 0.1mol/L of ascorbic acid solution.
A kind of high activity of the present invention has the preparation method of the cube nano Pd catalyst of meso-hole structure, step
The addition volume of palladium salt precursor solution is 2~8mL in 2, and the addition volume of 3- methyl-hexadecyl imidazole solution is
The addition volume of 0.05~0.5mL, deionized water are 27.5~56.95mL, and the addition volume of ascorbic acid solution is 1~4mL.
A kind of high activity of the present invention has the preparation method of the cube nano Pd catalyst of meso-hole structure, step
The addition volume of palladium salt precursor solution is 5mL in 2, and the addition volume of 3- methyl-hexadecyl imidazole solution is
The addition volume of 0.1mL, deionized water are 42mL, and the addition volume of ascorbic acid solution is 2.5mL.
A kind of high activity of the present invention has the preparation method of the cube nano Pd catalyst of meso-hole structure, step
100~500r/min of speed of agitator, 60 DEG C of reaction temperature, reaction time 2h are controlled in 2.
A kind of high activity of the present invention has the preparation method of the cube nano Pd catalyst of meso-hole structure, step
Centrifugal rotational speed 12000rpm in 3, centrifugation time 4min.
A kind of high activity of the present invention have meso-hole structure cube nano Pd catalyst preparation method, go from
Sub- water washing 3 times, in the absolute ethyl alcohol of 10~100 times of volumes, ultrasonic disperse power is the sediment ultrasonic disperse after washing
10~20kHz, 10~20min of ultrasonic time.
There is a kind of high activity of the present invention the preparation method of the cube nano Pd catalyst of meso-hole structure to prepare
High activity have meso-hole structure cube nano Pd catalyst, the high activity have meso-hole structure cube nanometer
Palladium catalyst has cube structure, is uniformly dispersed, there are meso-hole structures inside cube structure.
A kind of high activity of the present invention has the preparation method of the cube nano Pd catalyst of meso-hole structure, in nothing
Under the premise of crystal seed, in 3- methyl-hexadecyl imidazoles (1-hexadecyl-3-methylimidazolium
Bromide, HMIB) in the presence of, being made has cubic pattern, and inside is there are the palladium nanocatalyst of meso-hole structure, interior
Portion meso-hole structure aperture is 1.7~2.4nm, and compared with conventional method, palladium nano cubic body catalyst produced by the present invention has
More active sites show greater activity in methanol electrooxidation reaction.
A kind of high activity of the present invention has the preparation method of the cube nano Pd catalyst of meso-hole structure, 3- first
Base-hexadecyl imidazoles is protective agent, and ascorbic acid (Ascorbic acid, AA) is reducing agent, 3- methyl-bromination ten
Six alkyl imidazoles are with palladium presoma ions binding at forerunner's compound, and after reducing agent ascorbic acid is added, forerunner's compound is delayed
Slowly it is reduced into Pd0And small range assembles to form nucleus.As reduction reaction continues, Pd0The continuous deposition growing on nucleus,
Ultimately form the cube nano Pd catalyst with meso-hole structure.
Description of the drawings
Fig. 1 is the cube nano Pd catalyst that high activity prepared by one method of specific implementation mode has meso-hole structure
40000 times of TEM photos；
Fig. 2 is the cube nano Pd catalyst that high activity prepared by one method of specific implementation mode has meso-hole structure
150000 times of TEM photos；
Fig. 3 is the cube nano Pd catalyst that high activity prepared by one method of specific implementation mode has meso-hole structure
HRTEM photos；
Fig. 4 is the cube nano Pd catalyst that high activity prepared by one method of specific implementation mode has meso-hole structure
XRD spectrum；
Fig. 5 be one method of specific implementation mode prepare high activity have meso-hole structure cube nano Pd catalyst and
The methanol oxidation cycle volt-ampere correlation curve of commercial Pd/C catalyst.
Specific implementation mode
Specific implementation mode one：
A kind of preparation method of cube nano Pd catalyst of the high activity with meso-hole structure, includes the following steps：
Palladium salt, 3- methyl-hexadecyl imidazoles, ascorbic acid are dissolved in deionized water by step 1 respectively, configuration
At palladium salt precursor solution, 3- methyl-hexadecyl imidazole solution, ascorbic acid solution, for use；
Step 2, the palladium salt precursor solution that step 1 has been configured and 3- methyl-hexadecyl imidazole solution are added
To 10min is stirred in deionized water, ascorbic acid solution is added, controlling reaction temperature is 60 DEG C under stirring condition, when reaction
Between 2h, the palladium salt precursor solution, 3- methyl-hexadecyl imidazole solution, ascorbic acid solution and deionized water
Volume ratio be 5：0.1：2.5：42, the solution for later use after reaction；
Solution after step 2 reaction is carried out centrifugal treating by step 3, removes supernatant, 3 institutes are washed with deionized
Sediment is obtained, by the sediment ultrasonic disperse after washing in absolute ethyl alcohol, the high activity for being made described has meso-hole structure
Cube nano Pd catalyst.
A kind of high activity described in present embodiment has the preparation method of the cube nano Pd catalyst of meso-hole structure,
Palladium salt described in step 1 is Na2PdCl4。
A kind of high activity described in present embodiment has the preparation method of the cube nano Pd catalyst of meso-hole structure,
A concentration of 0.01mol/L, 3- methyl-hexadecyl imidazole solution of palladium salt precursor solution is a concentration of in step 1
A concentration of 0.1mol/L of 0.1mol/L, ascorbic acid solution.
A kind of high activity described in present embodiment has the preparation method of the cube nano Pd catalyst of meso-hole structure,
The addition volume of palladium salt precursor solution is 5mL in step 2, and the addition volume of 3- methyl-hexadecyl imidazole solution is
The addition volume of 0.1mL, deionized water are 42mL, and the addition volume of ascorbic acid solution is 2.5mL.
A kind of high activity described in present embodiment has the preparation method of the cube nano Pd catalyst of meso-hole structure,
Speed of agitator 100r/min, 60 DEG C of reaction temperature, reaction time 2h are controlled in step 2.
A kind of high activity described in present embodiment has the preparation method of the cube nano Pd catalyst of meso-hole structure,
Centrifugal rotational speed 12000rpm in step 3, centrifugation time 4min.
A kind of high activity described in present embodiment has the preparation method of the cube nano Pd catalyst of meso-hole structure,
Deionized water is washed 3 times, and in the absolute ethyl alcohol of 30 times of volumes, ultrasonic disperse power is the sediment ultrasonic disperse after washing
10kHz, ultrasonic time 15min.
A kind of high activity described in present embodiment has the preparation method of the cube nano Pd catalyst of meso-hole structure
There is the high activity of preparation the cube nano Pd catalyst of meso-hole structure, the high activity to have the cube of meso-hole structure
Nano Pd catalyst has cube structure, and there are meso-hole structures inside cube structure.
A kind of high activity described in present embodiment has the preparation method of the cube nano Pd catalyst of meso-hole structure
It is high activity prepared by present embodiment method that the high activity of preparation, which has the cube nano Pd catalyst of meso-hole structure, Fig. 1,
40,000 times of TEM photos, Fig. 2 of cube nano Pd catalyst with meso-hole structure are height prepared by present embodiment method
Activity has 150,000 times of TEM photos of the cube nano Pd catalyst of meso-hole structure, from Fig. 1 and Fig. 2, it can be seen that high living
Property be uniformly dispersed with the cube nano Pd catalyst of meso-hole structure, there is cube structure, exist inside cube structure
Meso-hole structure.
Fig. 3 is the cube nano Pd catalyst that high activity prepared by present embodiment method has meso-hole structure
HRTEM photos, it can be seen that high activity has the mesoporous knot in inside of the cube nano Pd catalyst of meso-hole structure from Fig. 3
Structure aperture is 1.7~2.4nm.
Fig. 4 is the XRD for the cube nano Pd catalyst that high activity prepared by present embodiment method has meso-hole structure
Collection of illustrative plates, it can be seen that there are high activity the cube nano Pd catalyst surface existing defects of meso-hole structure and height to refer to from Fig. 4
Number crystal face, has 111,200,220,311,222 crystal faces, can provide more active sites for catalysis reaction.
Fig. 5 is cube nano Pd catalyst and the commercialization that high activity prepared by present embodiment method has meso-hole structure
The methanol oxidation cycle volt-ampere correlation curve of Pd/C catalyst.The cube with meso-hole structure prepared using present embodiment
Nano Pd catalyst and commercial palladium carbon hydrogenation catalyst Pd/C catalysis methanol electrochemical oxidation reactions, are tested by cyclic voltammetry
The catalytic activity of each catalyst.Wherein commercialization palladium carbon hydrogenation catalyst Pd/C is produced by Sinopharm Chemical Reagent Co., Ltd.,
Palladium load capacity is 5wt%, and palladium particle is in sphere, average grain diameter 4.7nm in Pd/C catalyst.Take 10 μ L present embodiment systems
It is standby with meso-hole structure cube nano Pd catalyst (a concentration of 1.67mg/mL) or commercialization Pd/C catalyst (Pd amounts with
Palladium nano cubic body catalyst is consistent) glassy carbon electrode surface is dropped to, at room temperature after natural drying, then take the perfluor of 10 μ L 0.5%
Sulfonic acid (Nafion) solution drips thereon, equally dries at room temperature, the glass carbon working electrode after being modified.By itself and platinum disk electricity
Pole and saturated calomel electrode form three-electrode system, and cyclic voltammetric is carried out in 1mol/L KOH solutions and 1mol/L methanol solutions
Sweep test (CV), scanning potential range are -0.9~0.1V, sweep speed 50mV/s, and the CV curves after record is stablized are divided
Analysis, as shown in Figure 5.Logical N before all solution testings2For gas 30min to remove the dissolved oxygen in solution, water used is ultrapure
Water.It can be seen that high activity prepared by present embodiment has the cube nano Pd catalyst of meso-hole structure in first from Fig. 5
All have higher catalytic activity in alcohol oxidation reaction, and commercialization Pd/C catalyst for methanol in alkaline medium oxidation not
Apparent catalytic activity is shown, reason is on space structure that the sequence of the atom active on polyhedron is vertex>Rib>Face,
And obvious shortcoming and high activity crystal face is not present in the palladium nano-particles cluster-shaped spherical in shape in Pd/C, surface.In conjunction with Fig. 1 and Fig. 2
The pattern and surface texture of middle palladium nanocube, compared with Pd/C catalyst, high activity prepared by present embodiment has Jie
The surface existing defects and high miller index surface of the cube nano Pd catalyst of pore structure, and there are meso-hole structure (apertures for inside
For 1.7~2.4nm), more active sites are provided for reaction, thus with higher in methanol electrooxidation reaction
Catalytic activity.It is as shown in table 1 that methanol electrooxidation reacts the comparison of anodic peak current density：
1 methanol electrooxidation of table reacts anodic peak current density contrast table
High activity prepared by present embodiment method has the cube nano Pd catalyst anodic peak current of meso-hole structure
Density 13.22mA cm-2, the anodic peak current density of commercial Pd/C catalyst is 0mA cm-2。
Specific implementation mode two：
A kind of preparation method of cube nano Pd catalyst of the high activity with meso-hole structure, includes the following steps：
Palladium salt, 3- methyl-hexadecyl imidazoles, ascorbic acid are dissolved in deionized water by step 1 respectively, configuration
At palladium salt precursor solution, 3- methyl-hexadecyl imidazole solution, ascorbic acid solution, for use；
Step 2, the palladium salt precursor solution that step 1 has been configured and 3- methyl-hexadecyl imidazole solution are added
To 10min is stirred in deionized water, ascorbic acid solution is added, controlling reaction temperature is 60 DEG C under stirring condition, when reaction
Between 2h, the palladium salt precursor solution, 3- methyl-hexadecyl imidazole solution, ascorbic acid solution and deionized water
Volume ratio be 5：0.5：3：42, the solution for later use after reaction；
Solution after step 2 reaction is carried out centrifugal treating by step 3, removes supernatant, 3 institutes are washed with deionized
Sediment is obtained, by the sediment ultrasonic disperse after washing in absolute ethyl alcohol, the high activity for being made described has meso-hole structure
Cube nano Pd catalyst.
A kind of high activity described in present embodiment has the preparation method of the cube nano Pd catalyst of meso-hole structure,
Palladium salt described in step 1 is H2PdC14。
A kind of high activity described in present embodiment has the preparation method of the cube nano Pd catalyst of meso-hole structure,
A concentration of 0.01mol/L, 3- methyl-hexadecyl imidazole solution of palladium salt precursor solution is a concentration of in step 1
A concentration of 0.1mol/L of 0.1mol/L, ascorbic acid solution.
A kind of high activity described in present embodiment has the preparation method of the cube nano Pd catalyst of meso-hole structure,
The addition volume of palladium salt precursor solution is 5mL in step 2, and the addition volume of 3- methyl-hexadecyl imidazole solution is
The addition volume of 0.5mL, deionized water are 42mL, and the addition volume of ascorbic acid solution is 3mL.
A kind of high activity described in present embodiment has the preparation method of the cube nano Pd catalyst of meso-hole structure,
Speed of agitator 200r/min, 70 DEG C of reaction temperature, reaction time 1h are controlled in step 2.
A kind of high activity described in present embodiment has the preparation method of the cube nano Pd catalyst of meso-hole structure,
Centrifugal rotational speed 12000rpm in step 3, centrifugation time 4min.
A kind of high activity described in present embodiment has the preparation method of the cube nano Pd catalyst of meso-hole structure,
Deionized water is washed 3 times, and in the absolute ethyl alcohol of 30 times of volumes, ultrasonic disperse power is the sediment ultrasonic disperse after washing
10kHz, ultrasonic time 15min.
Specific implementation mode three：
It takes 42mL deionized waters in 100mL flasks, the Na of 5mL 0.01mol/L is added thereto2PdC14Solution and
The HMIB solution of 0.3mL 0.1mol/L uniformly mixes 10min, and is preheated to 60 DEG C under magnetic stirring.Then 2.5mL is added
The AA solution of 0.1mol/L, reduction reaction 3h after removing supernatant, use acquired solution centrifugal treating (12000rpm, 4min)
Deionized water is washed obtains cube nano Pd catalyst of the high activity with meso-hole structure three times.The high activity of gained is had
There is the cube nano Pd catalyst ultrasonic disperse of meso-hole structure spare in 3mL absolute ethyl alcohols.
Specific implementation mode four：
It takes 42mL deionized waters in 100mL flasks, the Na of 5mL 0.01mol/L is added thereto2PdC14Solution and
The HMIB solution of 0.1mL 0.1mol/L uniformly mixes 10min, and is preheated to 40 DEG C under magnetic stirring.Then 2.5mL is added
The AA solution of 0.1mol/L, reduction reaction 2h after removing supernatant, use acquired solution centrifugal treating (12000rpm, 4min)
Deionized water is washed obtains cube nano Pd catalyst of the high activity with meso-hole structure three times.The high activity of gained is had
There is the cube nano Pd catalyst ultrasonic disperse of meso-hole structure spare in 3mL absolute ethyl alcohols.
Specific implementation mode five：
It takes 42mL deionized waters in 100mL flasks, the Na of 5mL 0.01mol/L is added thereto2PdC14Solution and
The HMIB solution of 0.1mL 0.1mol/L uniformly mixes 10min, and is preheated to 60 DEG C under magnetic stirring.Then 2.5mL is added
The AA solution of 0.1mol/L, reduction reaction 4h after removing supernatant, use acquired solution centrifugal treating (12000rpm, 4min)
Deionized water is washed obtains cube nano Pd catalyst of the high activity with meso-hole structure three times.The high activity of gained is had
There is the cube nano Pd catalyst ultrasonic disperse of meso-hole structure spare in 3mL absolute ethyl alcohols.
Specific implementation mode six：
A kind of preparation method of cube nano Pd catalyst of the high activity with meso-hole structure, includes the following steps：
Palladium salt, 3- methyl-hexadecyl imidazoles, ascorbic acid are dissolved in deionized water by step 1 respectively, configuration
At palladium salt precursor solution, 3- methyl-hexadecyl imidazole solution, ascorbic acid solution, for use；
Step 2, the palladium salt precursor solution that step 1 has been configured and 3- methyl-hexadecyl imidazole solution are added
To 10min is stirred in deionized water, ascorbic acid solution is added, controlling reaction temperature is 50 DEG C under stirring condition, when reaction
Between 1h, the palladium salt precursor solution, 3- methyl-hexadecyl imidazole solution, ascorbic acid solution and deionized water
Volume ratio be 5：0.05：2：42, the solution for later use after reaction；
Solution after step 2 reaction is carried out centrifugal treating by step 3, removes supernatant, 3 institutes are washed with deionized
Sediment is obtained, by the sediment ultrasonic disperse after washing in absolute ethyl alcohol, the high activity for being made described has meso-hole structure
Cube nano Pd catalyst.
A kind of high activity described in present embodiment has the preparation method of the cube nano Pd catalyst of meso-hole structure,
Palladium salt described in step 1 is K2PdC14。
A kind of high activity described in present embodiment has the preparation method of the cube nano Pd catalyst of meso-hole structure,
A concentration of 0.01mol/L, 3- methyl-hexadecyl imidazole solution of palladium salt precursor solution is a concentration of in step 1
A concentration of 0.1mol/L of 0.1mol/L, ascorbic acid solution.
A kind of high activity described in present embodiment has the preparation method of the cube nano Pd catalyst of meso-hole structure,
The addition volume of palladium salt precursor solution is 5mL in step 2, and the addition volume of 3- methyl-hexadecyl imidazole solution is
The addition volume of 0.05mL, deionized water are 42mL, and the addition volume of ascorbic acid solution is 2mL.
A kind of high activity described in present embodiment has the preparation method of the cube nano Pd catalyst of meso-hole structure,
Speed of agitator 200r/min, 50 DEG C of reaction temperature, reaction time 1h are controlled in step 2.
A kind of high activity described in present embodiment has the preparation method of the cube nano Pd catalyst of meso-hole structure,
Centrifugal rotational speed 12000rpm in step 3, centrifugation time 4min.
A kind of high activity described in present embodiment has the preparation method of the cube nano Pd catalyst of meso-hole structure,
Deionized water is washed 3 times, and in the absolute ethyl alcohol of 30 times of volumes, ultrasonic disperse power is the sediment ultrasonic disperse after washing
10kHz, ultrasonic time 15min.
Specific implementation mode seven：
A kind of preparation method of cube nano Pd catalyst of the high activity with meso-hole structure, includes the following steps：
Palladium salt, 3- methyl-hexadecyl imidazoles, ascorbic acid are dissolved in deionized water by step 1 respectively, configuration
At palladium salt precursor solution, 3- methyl-hexadecyl imidazole solution, ascorbic acid solution, for use；
Step 2, the palladium salt precursor solution that step 1 has been configured and 3- methyl-hexadecyl imidazole solution are added
To 10min is stirred in deionized water, ascorbic acid solution is added, controlling reaction temperature is 70 DEG C under stirring condition, when reaction
Between 30min, the palladium salt precursor solution, 3- methyl-hexadecyl imidazole solution, ascorbic acid solution and deionization
The volume ratio of water is 5：0.3：3：42, the solution for later use after reaction；
Solution after step 2 reaction is carried out centrifugal treating by step 3, removes supernatant, 3 institutes are washed with deionized
Sediment is obtained, by the sediment ultrasonic disperse after washing in absolute ethyl alcohol, the high activity for being made described has meso-hole structure
Cube nano Pd catalyst.
A kind of high activity described in present embodiment has the preparation method of the cube nano Pd catalyst of meso-hole structure,
Palladium salt described in step 1 is Pd (NO3)2。
A kind of high activity described in present embodiment has the preparation method of the cube nano Pd catalyst of meso-hole structure,
A concentration of 0.01mol/L, 3- methyl-hexadecyl imidazole solution of palladium salt precursor solution is a concentration of in step 1
A concentration of 0.1mol/L of 0.1mol/L, ascorbic acid solution.
A kind of high activity described in present embodiment has the preparation method of the cube nano Pd catalyst of meso-hole structure,
The addition volume of palladium salt precursor solution is 5mL in step 2, and the addition volume of 3- methyl-hexadecyl imidazole solution is
The addition volume of 0.3mL, deionized water are 42mL, and the addition volume of ascorbic acid solution is 3mL.
A kind of high activity described in present embodiment has the preparation method of the cube nano Pd catalyst of meso-hole structure,
Speed of agitator 200r/min, 70 DEG C of reaction temperature, reaction time 30min are controlled in step 2.
A kind of high activity described in present embodiment has the preparation method of the cube nano Pd catalyst of meso-hole structure,
Centrifugal rotational speed 12000rpm in step 3, centrifugation time 4min.
A kind of high activity described in present embodiment has the preparation method of the cube nano Pd catalyst of meso-hole structure,
Deionized water is washed 3 times, and in the absolute ethyl alcohol of 30 times of volumes, ultrasonic disperse power is the sediment ultrasonic disperse after washing
10kHz, ultrasonic time 15min.
Specific implementation mode two, four, five, six, seven reacts anode peak with the methanol electrooxidation of commercialization Pd/C catalyst
Current density comparison is as shown in table 2：
2 methanol electrooxidation of table reacts anodic peak current density contrast table
Palladium nano cubic body catalyst made from two, four, five, six, seven method of specific implementation mode has more activity
Site shows greater activity in methanol electrooxidation reaction, and the anodic peak current density of commercialization Pd/C catalyst is
0mA cm-2。
Claims (9)
1. a kind of high activity has the preparation method of the cube nano Pd catalyst of meso-hole structure, it is characterised in that：Including such as
Lower step：
Palladium salt, 3- methyl-hexadecyl imidazoles, ascorbic acid are dissolved in deionized water by step 1 respectively, are configured to palladium
Salt precursor liquid solution, 3- methyl-hexadecyl imidazole solution, ascorbic acid solution, for use；
Palladium salt precursor solution and 3- methyl-hexadecyl imidazole solution that step 1 has configured are added to by step 2
5~15min is stirred in ionized water, adds ascorbic acid solution, and controlling reaction temperature is 40~70 DEG C under stirring condition, reaction
0.5~4h of time, the palladium salt precursor solution, 3- methyl-hexadecyl imidazole solution, ascorbic acid solution and goes
The volume ratio of ionized water is 2~8：0.05~0.5：1~4：27.5~56.95, the solution for later use after reaction；
Solution after step 2 reaction is carried out centrifugal treating by step 3, removes supernatant, 3~5 gained are washed with deionized
Sediment, by the sediment ultrasonic disperse after washing in absolute ethyl alcohol, the high activity for being made described has the vertical of meso-hole structure
Cube nano Pd catalyst.
2. a kind of high activity according to claim 1 has the preparation side of the cube nano Pd catalyst of meso-hole structure
Method, it is characterised in that：Palladium salt described in step 1 is Na2PdCl4、K2PdCl4、H2PdCl4、Pd(NO3)2In any one.
3. a kind of high activity according to claim 1 has the preparation side of the cube nano Pd catalyst of meso-hole structure
Method, it is characterised in that：A concentration of 0.01mol/L, 3- methyl-hexadecyl imidazoles of palladium salt precursor solution in step 1
A concentration of 0.1mol/L of solution, a concentration of 0.1mol/L of ascorbic acid solution.
4. a kind of high activity according to claim 1 has the preparation side of the cube nano Pd catalyst of meso-hole structure
Method, it is characterised in that：The addition volume of palladium salt precursor solution is 2~8mL, 3- methyl-hexadecyl imidazoles in step 2
The addition volume of solution is 0.05~0.5mL, and the addition volume of deionized water is 27.5~56.95mL, ascorbic acid solution
Addition volume is 1~4mL.
5. a kind of high activity according to claim 1 or 4 has the preparation of the cube nano Pd catalyst of meso-hole structure
Method, it is characterised in that：The addition volume of palladium salt precursor solution is 5mL, 3- methyl-hexadecyl imidazoles in step 2
The addition volume of solution is 0.1mL, and the addition volume of deionized water is 42mL, and the addition volume of ascorbic acid solution is 2.5mL.
6. a kind of high activity according to claim 1 has the preparation side of the cube nano Pd catalyst of meso-hole structure
Method, it is characterised in that：100~500r/min of speed of agitator, 60 DEG C of reaction temperature, reaction time 2h are controlled in step 2.
7. a kind of high activity according to claim 1 has the preparation side of the cube nano Pd catalyst of meso-hole structure
Method, it is characterised in that：Centrifugal rotational speed 12000rpm in step 3, centrifugation time 4min.
8. a kind of high activity according to claim 1 has the preparation side of the cube nano Pd catalyst of meso-hole structure
Method, it is characterised in that：Deionized water is washed 3 times, and the sediment ultrasonic disperse after washing is in the absolute ethyl alcohol of 10~100 times of volumes
In, ultrasonic disperse power is 10~20kHz, 10~20min of ultrasonic time.
9. a kind of high activity described in a kind of one of claim 1-8 has the system of the cube nano Pd catalyst of meso-hole structure
High activity prepared by Preparation Method has the cube nano Pd catalyst of meso-hole structure, it is characterised in that：The high activity tool
There is the cube nano Pd catalyst of meso-hole structure that there is cube structure, there are meso-hole structures inside cube structure.
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| CN112002914A (en) * | 2020-08-21 | 2020-11-27 | 西安工业大学 | Reticular palladium nanowire with abundant surface defects and preparation method and application thereof |
| CN113560593A (en) * | 2021-07-20 | 2021-10-29 | 太原理工大学 | Preparation method of two-dimensional Pd nano-sieve rich in catalytic activity boundary |
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Application publication date: 20181019 |