CN108500256A - The hollow porous PdRh nano bowls preparation method of one kind and its resulting materials and application - Google Patents
The hollow porous PdRh nano bowls preparation method of one kind and its resulting materials and application Download PDFInfo
- Publication number
- CN108500256A CN108500256A CN201810426851.0A CN201810426851A CN108500256A CN 108500256 A CN108500256 A CN 108500256A CN 201810426851 A CN201810426851 A CN 201810426851A CN 108500256 A CN108500256 A CN 108500256A
- Authority
- CN
- China
- Prior art keywords
- pdrh
- hollow porous
- preparation
- nano
- bowls
- 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
- 238000002360 preparation method Methods 0.000 title claims abstract description 58
- 239000000463 material Substances 0.000 title claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000002243 precursor Substances 0.000 claims abstract description 26
- 150000003839 salts Chemical class 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 239000002270 dispersing agent Substances 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- 238000006056 electrooxidation reaction Methods 0.000 claims abstract description 4
- 238000005119 centrifugation Methods 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims abstract description 3
- 239000006227 byproduct Substances 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 70
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 17
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 17
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 17
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 16
- 239000004202 carbamide Substances 0.000 claims description 16
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 claims description 15
- 229910002093 potassium tetrachloropalladate(II) Inorganic materials 0.000 claims description 8
- 229910002666 PdCl2 Inorganic materials 0.000 claims description 7
- 229910003244 Na2PdCl4 Inorganic materials 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical group [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 238000007254 oxidation reaction Methods 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 52
- 235000019441 ethanol Nutrition 0.000 description 28
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 26
- 239000000047 product Substances 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 13
- 239000007788 liquid Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- 238000002604 ultrasonography Methods 0.000 description 13
- 238000001291 vacuum drying Methods 0.000 description 13
- 101100116420 Aedes aegypti DEFC gene Proteins 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/464—Rhodium
-
- B01J35/33—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
- B22F1/0549—Hollow particles, including tubes and shells
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
- B22F2009/245—Reduction reaction in an Ionic Liquid [IL]
Abstract
The invention discloses a kind of hollow porous PdRh nano bowls preparation method and its resulting materials and application of the material as ethanol electrooxidation catalysts, the preparation method includes taking Pd salt precursors body and Rh salt precursor bodies, it is added in solvent and is uniformly mixed simultaneously with pattern directed agents and dispersant, it is alkalinity to adjust mixed solution, then hydro-thermal reaction is carried out, by product centrifugation, washing, drying, you can obtain the hollow porous PdRh nano bowls.Compared with traditional preparation method, the present invention prepares hollow porous PdRh nano bowls by one step hydro thermal method, and simple process is easy, easy to operation, is conducive to large-scale production.And the have apparent hollow porous structure, average grain diameter of the hollow porous PdRh nano bowls of gained are 22 ± 5.0nm.Therefore, the hollow porous PdRh nano bowls that the method for the present invention is prepared have many advantages, such as that large specific surface area, active site are more, and higher catalytic activity and stability are shown when being applied to catalysis ethanol oxidation reaction.
Description
Technical field
The present invention relates to a kind of hollow porous PdRh nano bowls preparation method and its resulting materials and applications, belong to PdRh
Technical field of nano material.
Background technology
Direct Ethanol Fuel Cell (DEFCs) is concerned by people gradually, is had the following advantages mainly due to it：(1)
Direct Ethanol Fuel Cell has relative to the higher energy density of methanol (8kWh kg-1)；(2) ethyl alcohol is almost nontoxic；
(3) ethyl alcohol is readily available in nature, can be directly obtained from plant fermentation；(4) discharge product be water and carbon dioxide,
It is environmentally friendly.Therefore, DEFCs not only has theoretically researching value, and has the potentiality of good practical application.
The DEFCs run under alkaline condition has faster oxidation of ethanol dynamics, and alkaline condition can be reduced and be urged
The dissolving of agent.In addition, compared with Pt, relatively inexpensive Pd has the oxidation of better catalysis ethanol anti-under alkaline condition
The activity and stability answered.But Pd remains noble metal and the catalytic activity of pure Pd still cannot reach direct alcohol fuel
The application request of battery, therefore also need to further develop novel Pd base catalyst.Currently, hollow porous structure
The synthetic route of noble metal is mostly more complicated, and yield is not high and cannot prepare on a large scale.
Invention content
Goal of the invention：In view of the above technical problems, it is an object of the invention to propose a kind of hollow porous PdRh nano bowls
Preparation method, and the application of the PdRh nano bowls that are prepared as ethanol electrooxidation catalysts has excellent
Catalytic performance.
Technical solution：The present invention adopts the following technical scheme that：
A kind of hollow porous PdRh nano bowls preparation method, including Pd salt precursors body and Rh salt precursor bodies are taken, with pattern
Directed agents and dispersant, which are added simultaneously in solvent, to be uniformly mixed, and it is alkalinity to adjust mixed solution, then carries out hydro-thermal reaction, will produce
Object centrifugation, washing, drying, you can obtain the hollow porous PdRh nano bowls.
As preferred：
The solvent is deionized water, and the pattern directed agents are urea, and the dispersant is polyvinylpyrrolidone
(PVP) (preferably average molecular weight is Mw=30000), the adjusting mixed solution is that alkalinity is adjusted using NaOH solution
Section.
The Pd salt precursors body is K2PdCl4、Na2PdCl4Or PdCl2, the Rh salt precursors body is RhCl3。
The molar ratio of the Pd salt precursors body and Rh salt precursor bodies is (1~10):1.
The Pd salt precursors body and the molar ratio of pattern directed agents are (0.0625~2):1.
The molar ratio of the Pd salt precursors body and dispersant is (15~60):1.
The adjusting mixed solution is alkalinity, that is, it is 7~13 to adjust pH value.
The temperature of the hydro-thermal reaction is 140~220 DEG C, and the reaction time is 1~12h.
The present invention also provides the hollow porous PdRh nano bowls materials obtained by the preparation method, can be used as ethyl alcohol
The catalyst of electro-oxidation reaction, catalytic performance are excellent.
The method of the present invention introduces other metals Rh and forms alloy structure, can adjust the electronic state of Pd, since group divides it
Between synergistic effect, catalytic performance can be significantly increased.Wherein, it due to the hydrophily of Rh metals, can be easily absorbing
Hydrone forms more hydroxyl species, is conducive to the removing for poisoning species, improves the anti-poisoning ability of catalyst.Rh is one
The very promising catalyst of kind, it has good corrosion resistance and stability, and is conducive to second during electrocatalytic oxidation
The fracture of alcohol C-C keys, improves the dynamics of reaction.
Other than component regulates and controls, Morphological control is also an important factor for influencing catalytic performance.Gained of the invention is hollow more
There is the nanostructure in hole unique structural advantage, the specific surface area with bigger to be capable of providing more Adsorptions
Point accelerates the transmission and diffusion of substance, improves kinetics.
Therefore, the bubble that the method for the present invention is generated using urea is as soft template, the hollow porous PdRh of a step hydrothermal synthesis
The method of nano bowl.This method is simple for process, can a step obtain final product, and can be prepared with magnanimity.By obtained product
Applied to catalysis ethanol oxidation reaction, there is good catalytic performance.
Technique effect：Compared with traditional preparation method, the present invention prepares hollow porous PdRh by one step hydro thermal method and receives
Rice bowl, simple process is easy, easy to operation, is conducive to large-scale production.And the hollow porous PdRh nano bowls of gained have it is bright
Aobvious hollow porous structure, average grain diameter are 22 ± 5.0nm.Therefore, the hollow porous PdRh that the method for the present invention is prepared
Nano bowl has many advantages, such as that large specific surface area, active site are more, shown when being applied to catalysis ethanol oxidation reaction compared with
High catalytic activity and stability.
Description of the drawings
Fig. 1：A, b are the HRTEM figures of hollow porous PdRh nano bowls under different amplification respectively；
Fig. 2：A, b are the STEM figures of hollow porous PdRh nano bowls under different amplification respectively；
Fig. 3：The XRD spectrum of hollow porous PdRh nano bowls；
Fig. 4：A, b are the XPS collection of illustrative plates of hollow porous PdRh nano bowls；
Fig. 5：Hollow porous PdRh nano bowls and the commercialization black electro catalytic activity comparison diagrams to alkaline ethanol of Pd.
Specific implementation mode
Technical solutions according to the invention are further described in detail below by specific embodiment, but it is necessary to
It points out that following embodiment is served only for the description to invention content, does not constitute limiting the scope of the invention.
Embodiment 1
A kind of hollow porous PdRh nano bowls are ultrafast, magnanimity preparation method, include the following steps：
1) preparation of reaction solution：It measures 8mL aqueous solutions and makees solvent in 20mL reaction kettle liners, 1mL0.1mol is added
L-1Urea liquid make pattern directed agents, 0.5mL 0.05mol L are added-1PdCl2With 0.5mL 0.05M RhCl3It is forerunner
Body, stirring 30 minutes after be added 50mg PVP (Mw=30000), ultrasound 30 minutes after with NaOH solution adjust pH value of solution=
12.
2) preparation of PdRh nano bowls：The reaction solution prepared is placed in 140 DEG C of baking oven and reacts 4h, after reaction
Black product ethyl alcohol：Acetone=1:Three times, vacuum drying 6h can be obtained hollow porous at room temperature for 1 solution supersound washing
PdRh nano bowls.
Embodiment 2
A kind of hollow porous PdRh nano bowls are ultrafast, magnanimity preparation method, include the following steps：
1) preparation of reaction solution：It measures 7mL aqueous solutions and makees solvent in 20mL reaction kettle liners, 1mL0.1mol is added
L-1Urea liquid make pattern directed agents, 1mL 0.05mol L are added-1PdCl2With 1mL 0.05M RhCl3Presoma is done,
50mg PVP (Mw=30000) are added after stirring 30 minutes, ultrasound adjusts pH value of solution=12. after 30 minutes with NaOH solution
2) preparation of PdRh nano bowls：The reaction solution prepared is placed in 140 DEG C of baking oven and reacts 4h, after reaction
Black product ethyl alcohol：Acetone=1:Three times, vacuum drying 6h can be obtained hollow porous at room temperature for 1 solution supersound washing
PdRh nano bowls.
Embodiment 3
A kind of hollow porous PdRh nano bowls are ultrafast, magnanimity preparation method, include the following steps：
1) preparation of reaction solution：It measures 7mL aqueous solutions and makees solvent in 20mL reaction kettle liners, 1mL0.1mol is added
L-1Urea liquid make pattern directed agents, 1.5mL 0.05mol L are added-1PdCl2With 0.5mL 0.05M RhCl3It is forerunner
Body, stirring 30 minutes after be added 50mg PVP (Mw=30000), ultrasound 30 minutes after with NaOH solution adjust pH value of solution=
12.
2) preparation of PdRh nano bowls：The reaction solution prepared is placed in 140 DEG C of baking oven and reacts 4h, after reaction
Black product ethyl alcohol：Acetone=1:Three times, vacuum drying 6h can be obtained hollow porous at room temperature for 1 solution supersound washing
PdRh nano bowls.
Embodiment 4
A kind of hollow porous PdRh nano bowls are ultrafast, magnanimity preparation method, include the following steps：
1) preparation of reaction solution：Measurement 7mL aqueous solutions are made solvent and are answered in kettle liner in 20mL, and 1mL 0.1mol are added
L-1Urea liquid make pattern directed agents, 1mL 0.05mol L are added-1K2PdCl4With 1mL 0.05M RhCl3It is forerunner
Body, stirring 30 minutes after be added 50mg PVP (Mw=30000), ultrasound 30 minutes after with NaOH solution adjust pH value of solution=
12.
2) preparation of PdRh nano bowls：The reaction solution prepared is placed in 140 DEG C of baking oven and reacts 4h, after reaction
Black product ethyl alcohol：Acetone=1:Three times, vacuum drying 6h can be obtained hollow porous at room temperature for 1 solution supersound washing
PdRh nano bowls.
Embodiment 5
A kind of hollow porous PdRh nano bowls are ultrafast, magnanimity preparation method, include the following steps：
1) preparation of reaction solution：It measures 7mL aqueous solutions and makees solvent in 20mL reaction kettle liners, 1mL0.1mol is added
L-1Urea liquid make pattern directed agents, 1.5mL 0.05mol L are added-1K2PdCl4With 0.5mL 0.05M RhCl3Before doing
Body is driven, 50mg PVP (Mw=30000) are added in stirring after 30 minutes, ultrasound adjusts pH value of solution after 30 minutes with NaOH solution
=12.
2) preparation of PdRh nano bowls：The reaction solution prepared is placed in 140 DEG C of baking oven and reacts 4h, after reaction
Black product ethyl alcohol：Acetone=1:Three times, vacuum drying 6h can be obtained hollow porous at room temperature for 1 solution supersound washing
PdRh nano bowls.
Embodiment 6
A kind of hollow porous PdRh nano bowls are ultrafast, magnanimity preparation method, include the following steps：
1) preparation of reaction solution：It measures 7mL aqueous solutions and makees solvent in 20mL reaction kettle liners, 1mL0.1mol is added
L-1Urea liquid make pattern directed agents, 1mL 0.05mol L are added-1Na2PdCl4With 1mL 0.05M RhCl3It is forerunner
Body, stirring 30 minutes after be added 50mg PVP (Mw=30000), ultrasound 30 minutes after with NaOH solution adjust pH value of solution=
12.
2) preparation of PdRh nano bowls：The reaction solution prepared is placed in 140 DEG C of baking oven and reacts 4h, after reaction
Black product ethyl alcohol：Acetone=1:Three times, vacuum drying 6h can be obtained hollow porous at room temperature for 1 solution supersound washing
PdRh nano bowls.
Embodiment 7
A kind of hollow porous PdRh nano bowls are ultrafast, magnanimity preparation method, include the following steps：
1) preparation of reaction solution：It measures 6mL aqueous solutions and makees solvent in 20mL reaction kettle liners, 2mL0.1mol is added
L-1Urea liquid make pattern directed agents, 1mL 0.05mol L are added-1PdCl2With 1mL 0.05M RhCl3Presoma is done,
50mg PVP (Mw=30000) are added after stirring 30 minutes, ultrasound adjusts pH value of solution=12. after 30 minutes with NaOH solution
2) preparation of PdRh nano bowls：The reaction solution prepared is placed in 140 DEG C of baking oven and reacts 4h, after reaction
Black product ethyl alcohol：Acetone=1:Three times, vacuum drying 6h can be obtained hollow porous at room temperature for 1 solution supersound washing
PdRh nano bowls.
Embodiment 8
A kind of hollow porous PdRh nano bowls are ultrafast, magnanimity preparation method, include the following steps：
1) preparation of reaction solution：It measures 6mL aqueous solutions and makees solvent in 20mL reaction kettle liners, 2mL0.1mol is added
L-1Urea liquid make pattern directed agents, 1mL 0.05mol L are added-1K2PdCl4With 1mL 0.05M RhCl3It is forerunner
Body, stirring 30 minutes after be added 50mg PVP (Mw=30000), ultrasound 30 minutes after with NaOH solution adjust pH value of solution=
12.
2) preparation of PdRh nano bowls：The reaction solution prepared is placed in 140 DEG C of baking oven and reacts 4h, after reaction
Black product ethyl alcohol：Acetone=1:Three times, vacuum drying 6h can be obtained hollow porous at room temperature for 1 solution supersound washing
PdRh nano bowls.
Embodiment 9
A kind of hollow porous PdRh nano bowls are ultrafast, magnanimity preparation method, include the following steps：
1) preparation of reaction solution：It measures 6mL aqueous solutions and makees solvent in 20mL reaction kettle liners, 2mL0.1mol is added
L-1Urea liquid make pattern directed agents, 1mL 0.05mol L are added-1Na2PdCl4With 1mL 0.05M RhCl3It is forerunner
Body, stirring 30 minutes after be added 50mg PVP (Mw=30000), ultrasound 30 minutes after with NaOH solution adjust pH value of solution=
12.
2) preparation of PdRh nano bowls：The reaction solution prepared is placed in 140 DEG C of baking oven and reacts 4h, after reaction
Black product ethyl alcohol：Acetone=1:Three times, vacuum drying 6h can be obtained hollow porous at room temperature for 1 solution supersound washing
PdRh nano bowls.
Embodiment 10
A kind of hollow porous PdRh nano bowls are ultrafast, magnanimity preparation method, include the following steps：
1) preparation of reaction solution：It measures 7mL aqueous solutions and makees solvent in 20mL reaction kettle liners, 1mL0.1mol is added
L-1Urea liquid make pattern directed agents, 1.5mL 0.05mol L are added-1K2PdCl4With 0.5mL 0.05M RhCl3Before doing
Body is driven, 50mg PVP (Mw=30000) are added in stirring after 30 minutes, ultrasound adjusts pH value of solution after 30 minutes with NaOH solution
=12.
2) preparation of PdRh nano bowls：The reaction solution prepared is placed in 180 DEG C of baking oven and reacts 4h, after reaction
Black product ethyl alcohol：Acetone=1:Three times, vacuum drying 6h can be obtained hollow porous at room temperature for 1 solution supersound washing
PdRh nano bowls.
Embodiment 11
A kind of hollow porous PdRh nano bowls are ultrafast, magnanimity preparation method, include the following steps：
1) preparation of reaction solution：It measures 7mL aqueous solutions and makees solvent in 20mL reaction kettle liners, 1mL0.1mol is added
L-1Urea liquid make pattern directed agents, 1.5mL 0.05mol L are added-1PdCl2With 0.5mL 0.05M RhCl3It is forerunner
Body, stirring 30 minutes after be added 50mg PVP (Mw=30000), ultrasound 30 minutes after with NaOH solution adjust pH value of solution=
12.
2) preparation of PdRh nano bowls：The reaction solution prepared is placed in 200 DEG C of baking oven and reacts 4h, after reaction
Black product ethyl alcohol：Acetone=1:Three times, vacuum drying 6h can be obtained hollow porous at room temperature for 1 solution supersound washing
PdRh nano bowls.
Embodiment 12
A kind of hollow porous PdRh nano bowls are ultrafast, magnanimity preparation method, include the following steps：
1) preparation of reaction solution：It measures 7mL aqueous solutions and makees solvent in 20mL reaction kettle liners, 1mL0.1mol is added
L-1Urea liquid make pattern directed agents, 1.5mL 0.05mol L are added-1K2PdCl4With 0.5mL 0.05M RhCl3Before doing
Body is driven, 50mg PVP (Mw=30000) are added in stirring after 30 minutes, ultrasound adjusts pH value of solution after 30 minutes with NaOH solution
=12.
2) preparation of PdRh nano bowls：The reaction solution prepared is placed in 200 DEG C of baking oven and reacts 4h, after reaction
Black product ethyl alcohol：Acetone=1:Three times, vacuum drying 6h can be obtained hollow porous at room temperature for 1 solution supersound washing
PdRh nano bowls.
Embodiment 13
A kind of hollow porous PdRh nano bowls are ultrafast, magnanimity preparation method, include the following steps：
1) preparation of reaction solution：It measures 7mL aqueous solutions and makees solvent in 20mL reaction kettle liners, 1mL0.1mol is added
L-1Urea liquid pattern directed agents, 1mL 0.05mol L are added-1K2PdCl4With 1mL 0.05M RhCl3Presoma is done,
50mg PVP (Mw=30000) are added after stirring 30 minutes, ultrasound adjusts pH value of solution=12. after 30 minutes with NaOH solution
2) preparation of PdRh nano bowls：The reaction solution prepared is placed in 200 DEG C of baking oven and reacts 6h, after reaction
Black product ethyl alcohol：Acetone=1:Three times, vacuum drying 6h can be obtained hollow porous at room temperature for 1 solution supersound washing
PdRh nano bowls.
Embodiment 14
It is same as Example 1, it the difference is that only as follows：
The molar ratio of Pd salt precursors body and Rh salt precursor bodies is 10:1；The molar ratio of Pd salt precursors body and pattern directed agents
Example is 0.0625:1；The molar ratio of Pd salt precursors body and dispersant is 15:1.
It is 7 to adjust pH value, and the temperature of hydro-thermal reaction is 220 DEG C, reaction time 1h.
Embodiment 15
It is same as Example 1, it the difference is that only as follows：
The molar ratio of Pd salt precursors body and Rh salt precursor bodies is 5:1；The molar ratio of Pd salt precursors body and pattern directed agents
Example is 2:1；The molar ratio of Pd salt precursors body and dispersant is 60:1.
It is 13 to adjust pH value, and the temperature of hydro-thermal reaction is 180 DEG C, reaction time 12h.
It using approach such as TEM, HRTEM, STEM, XRD and XPS prepared by above example hollow PdRh nanometers porous
Bowl carries out physical characterization.Catalyst prepared according to the methods of the invention is can be seen that from HRTEM (Fig. 1) and STEM (Fig. 2) collection of illustrative plates
It is a kind of hollow porous structure, and size is uniform, average grain diameter is 22 ± 5.0nm, therefore can provide the ratio table of bigger
Area and more active sites accelerate the transmission and diffusion of substance, improve kinetics.Fig. 3 is the XRD of PdRh nano bowls
Collection of illustrative plates, by being compared with standard diagram, it was demonstrated that being successfully formed for PdRh alloys.Fig. 4 is the XPS collection of illustrative plates of PdRh nano bowls, is shown
Show that Pd, Rh exist with zero-valent state in PdRh nano bowls, illustrates that presoma Pd (II), Rh (III) have been completely reduced respectively into zeroth order
Pd, zeroth order Rh.Fig. 5 is the electro catalytic activity comparison diagram of alkaline ethanol, as seen from the figure, black relative to commercialization Pd, PdRh
The take-off potential and spike potential of nano bowl are born move 0.25 and 0.05V respectively, and peak current is also that the black three times of Pd are more, it was demonstrated that
PdRh nano bowls have more excellent alcohol oxidation activity more black than commercialization Pd.
Claims (10)
1. a kind of hollow porous PdRh nano bowls preparation method, which is characterized in that including taking Pd salt precursors body and Rh salt precursors
Body is added in solvent with pattern directed agents and dispersant and is uniformly mixed simultaneously, and it is alkalinity to adjust mixed solution, then carries out hydro-thermal
Reaction, by product centrifugation, washing, drying, you can obtain the hollow porous PdRh nano bowls.
2. hollow porous PdRh nano bowls preparation method according to claim 1, which is characterized in that the solvent is to go
Ionized water, the pattern directed agents are urea, and the dispersant is polyvinylpyrrolidone (PVP), the adjusting mixed solution
For alkalinity it is adjusted using NaOH solution.
3. hollow porous PdRh nano bowls preparation method according to claim 1, which is characterized in that the Pd salt precursors
Body is K2PdCl4、Na2PdCl4Or PdCl2, the Rh salt precursors body is RhCl3。
4. hollow porous PdRh nano bowls preparation method according to claim 1, which is characterized in that the Pd salt precursors
The molar ratio of body and Rh salt precursor bodies is (1~10):1.
5. hollow porous PdRh nano bowls preparation method according to claim 1, which is characterized in that the Pd salt precursors
Body and the molar ratio of pattern directed agents are (0.0625~2):1.
6. hollow porous PdRh nano bowls preparation method according to claim 1, which is characterized in that the Pd salt precursors
The molar ratio of body and dispersant is (15~60):1.
7. hollow porous PdRh nano bowls preparation method according to claim 1, which is characterized in that the adjusting mixing
Solution is alkalinity, that is, it is 7~13 to adjust pH value.
8. hollow porous PdRh nano bowls preparation method according to claim 1, which is characterized in that the hydro-thermal reaction
Temperature be 140~220 DEG C, the reaction time be 1~12h.
9. the hollow porous PdRh nano bowls material obtained by any one of the claim 1-8 preparation methods.
10. application of the hollow porous PdRh nano bowls material as ethanol electrooxidation catalysts described in claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810426851.0A CN108500256A (en) | 2018-05-07 | 2018-05-07 | The hollow porous PdRh nano bowls preparation method of one kind and its resulting materials and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810426851.0A CN108500256A (en) | 2018-05-07 | 2018-05-07 | The hollow porous PdRh nano bowls preparation method of one kind and its resulting materials and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108500256A true CN108500256A (en) | 2018-09-07 |
Family
ID=63400266
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810426851.0A Pending CN108500256A (en) | 2018-05-07 | 2018-05-07 | The hollow porous PdRh nano bowls preparation method of one kind and its resulting materials and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108500256A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109802143A (en) * | 2019-01-18 | 2019-05-24 | 三峡大学 | A kind of preparation method and application of fuel cell 3D reticular structure PdRh alloy elctro-catalyst |
| CN110416563A (en) * | 2019-07-15 | 2019-11-05 | 三峡大学 | A kind of preparation method and application of fuel cell PdRh alloy elctro-catalyst |
| CN110586957A (en) * | 2019-09-29 | 2019-12-20 | 河南科技大学 | Preparation method of porous Pd hollow nanospheres in ionic liquid aqueous solution |
| CN111483971A (en) * | 2020-01-17 | 2020-08-04 | 杭州电子科技大学 | Two-axis symmetric porous cavity-shaped array structure and preparation method thereof |
| CN112397731A (en) * | 2020-11-13 | 2021-02-23 | 安徽大学 | Preparation of hollow PdCoP/C alloy electrocatalyst and application thereof in ethanol electrocatalytic oxidation |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7108773B2 (en) * | 2002-09-11 | 2006-09-19 | The Board Of Trustees Of The University Of Illinois | Solids supporting mass transfer for fuel cells and other applications and solutions and methods for forming |
| CN102019431A (en) * | 2010-09-30 | 2011-04-20 | 大连理工大学 | Metallic nano cluster/silicon dioxide hollow nuclear shell structured nanoparticles and preparation method thereof |
| CN102451688A (en) * | 2010-10-27 | 2012-05-16 | 中国科学院大连化学物理研究所 | Hollow nanocomposite oxide material and preparation thereof |
| CN104646025A (en) * | 2015-02-06 | 2015-05-27 | 江苏大学 | Preparation method of hollow Pt/Ni alloy and graphene aerogel compound material |
| CN104928518A (en) * | 2015-07-14 | 2015-09-23 | 北京航空航天大学 | Ultra-fine nano-porous metal and preparing method thereof |
| CN105149611A (en) * | 2015-09-18 | 2015-12-16 | 温州大学 | Hollow precious metal nanowire as well as preparation method and application thereof |
-
2018
- 2018-05-07 CN CN201810426851.0A patent/CN108500256A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7108773B2 (en) * | 2002-09-11 | 2006-09-19 | The Board Of Trustees Of The University Of Illinois | Solids supporting mass transfer for fuel cells and other applications and solutions and methods for forming |
| CN102019431A (en) * | 2010-09-30 | 2011-04-20 | 大连理工大学 | Metallic nano cluster/silicon dioxide hollow nuclear shell structured nanoparticles and preparation method thereof |
| CN102451688A (en) * | 2010-10-27 | 2012-05-16 | 中国科学院大连化学物理研究所 | Hollow nanocomposite oxide material and preparation thereof |
| CN104646025A (en) * | 2015-02-06 | 2015-05-27 | 江苏大学 | Preparation method of hollow Pt/Ni alloy and graphene aerogel compound material |
| CN104928518A (en) * | 2015-07-14 | 2015-09-23 | 北京航空航天大学 | Ultra-fine nano-porous metal and preparing method thereof |
| CN105149611A (en) * | 2015-09-18 | 2015-12-16 | 温州大学 | Hollow precious metal nanowire as well as preparation method and application thereof |
Non-Patent Citations (6)
| Title |
|---|
| CHIEN-TE HSIEH: "Bimetallic Pd–Rh nanoparticles onto reduced graphene oxide nanosheets as electrocatalysts for methanol oxidation", 《JOURNAL OF ELECTROANALYTICAL CHEMISTRY》 * |
| ERIK VESSELLI: "Ethanol Decomposition: C-C CleavageSelectivity on Rh(111", 《ARTICLES》 * |
| S.Y. SHEN: "Carbon supported PtRh catalysts for ethanol oxidation in alkaline direct ethanol fuel cell", 《HYDRIGEN ENERGY》 * |
| WANG, SB: "Pd-Rh Nanocrystals with Tunable Morphologies and Compositions as Efficient Catalysts toward SuzukiCross-Coupling Reactions", 《ACS CATALYSIS》 * |
| YE, WEI: "Controlled synthesis of bimetallic Pd-Rh nanoframes and nanoboxes with high catalytic performances", 《NANOSCALE》 * |
| 付更涛: "胺基分子铺助合成多孔贵金属纳米晶及其电催化性能", 《中国硕士学位论文全文数据库》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109802143A (en) * | 2019-01-18 | 2019-05-24 | 三峡大学 | A kind of preparation method and application of fuel cell 3D reticular structure PdRh alloy elctro-catalyst |
| CN110416563A (en) * | 2019-07-15 | 2019-11-05 | 三峡大学 | A kind of preparation method and application of fuel cell PdRh alloy elctro-catalyst |
| CN110416563B (en) * | 2019-07-15 | 2022-06-03 | 三峡大学 | Preparation method and application of PdRh alloy electrocatalyst for fuel cell |
| CN110586957A (en) * | 2019-09-29 | 2019-12-20 | 河南科技大学 | Preparation method of porous Pd hollow nanospheres in ionic liquid aqueous solution |
| CN110586957B (en) * | 2019-09-29 | 2022-05-10 | 河南科技大学 | Preparation method of porous Pd hollow nanospheres in ionic liquid aqueous solution |
| CN111483971A (en) * | 2020-01-17 | 2020-08-04 | 杭州电子科技大学 | Two-axis symmetric porous cavity-shaped array structure and preparation method thereof |
| CN112397731A (en) * | 2020-11-13 | 2021-02-23 | 安徽大学 | Preparation of hollow PdCoP/C alloy electrocatalyst and application thereof in ethanol electrocatalytic oxidation |
| CN112397731B (en) * | 2020-11-13 | 2022-02-11 | 安徽大学 | Preparation of hollow PdCoP/C alloy electrocatalyst and application thereof in ethanol electrocatalytic oxidation |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108500256A (en) | The hollow porous PdRh nano bowls preparation method of one kind and its resulting materials and application | |
| CN103022521A (en) | Palladium-cobalt/graphene nano electro-catalyst and preparation method thereof | |
| CN108598509A (en) | A kind of preparation method of Pt-Pd nuclear shell structure nanos catalyst | |
| WO2020107952A1 (en) | Efficient and stable stainless steel-based electrolytic water catalytic electrode and preparation method therefor and application thereof | |
| CN105810960B (en) | It is a kind of using nickel foam as the composite material and preparation method of matrix | |
| CN103531826A (en) | Direct-methanol fuel cell nano-porous structural film electrode construction method based on sacrificial template method | |
| CN108155392A (en) | A kind of preparation method of redox graphene load Pd-M nano-composite catalysts | |
| CN107482234A (en) | A kind of preparation method of the carbon material supported palladium-copper alloy fuel-cell catalyst of sulphur, nitrogen, cobalt codope | |
| CN110890559B (en) | Preparation method of carbonized wood loaded PdCo alloy composite electrocatalyst | |
| CN114045505B (en) | High-activity large-size electrolysis water hydrogen evolution electrode and pulse laser preparation method thereof | |
| CN110854396A (en) | PtAg nanocrystalline with porous double-hollow-sphere structure and preparation method and application thereof | |
| CN104888769A (en) | Preparation method of charcoal-supported palladium-silver nanometer composite catalyst for direct methanol fuel cells | |
| CN111893357B (en) | Self-supporting three-dimensional nano hierarchical pore high-entropy alloy electrolytic water material and preparation method thereof | |
| CN106910905A (en) | A kind of preparation method of carbon-supported nanometer palladium composite electrocatalyst | |
| CN105251509A (en) | Preparing method for Pt-Co flower-type nano-catalyst | |
| CN108110284B (en) | Method for directly preparing platinum nanocrystalline core-shell catalyst layer for fuel cell | |
| CN108682875A (en) | A kind of platinum controllable based on platinum carrying capacity-nano hollow carbon sphere catalyst and preparation method thereof | |
| CN113903934B (en) | Preparation method and application of porous Pd-PdO nanorods | |
| CN110180594A (en) | A kind of preparation method of elctro-catalyst | |
| CN111293323A (en) | Porous platinum-palladium nano cubic material, preparation method thereof and application thereof in catalyzing methanol oxidation | |
| CN102626617B (en) | Preparation method of porous silicon supported three-dimensional platinum nanometer catalyst | |
| CN109037706B (en) | Preparation method of multi-twisted atom palladium-copper alloy nanochain catalyst, product and application thereof | |
| CN109971172B (en) | One-step preparation method and application of palladium-silver alloy/polyaniline nanocomposite | |
| CN109590483B (en) | Preparation method of Ir nanowire with nano-holes, obtained material and application thereof | |
| CN110165227B (en) | PtAu nano catalyst with controllable active site spacing and preparation method thereof |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180907 |