CN111804316B - Super crystal cell with high catalytic activity and preparation method thereof - Google Patents
Super crystal cell with high catalytic activity and preparation method thereof Download PDFInfo
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- 210000002858 crystal cell Anatomy 0.000 title claims abstract description 36
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 210000004027 cell Anatomy 0.000 claims abstract description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 19
- 239000001257 hydrogen Substances 0.000 claims abstract description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 13
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 13
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 13
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 13
- 238000009826 distribution Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 5
- 238000004321 preservation Methods 0.000 claims description 14
- 229910008423 Si—B Inorganic materials 0.000 claims description 13
- 238000002425 crystallisation Methods 0.000 claims description 9
- 230000008025 crystallization Effects 0.000 claims description 9
- 230000001681 protective effect Effects 0.000 claims description 9
- 238000005868 electrolysis reaction Methods 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 abstract description 2
- 125000004429 atom Chemical group 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 229910000808 amorphous metal alloy Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1856—Phosphorus; Compounds thereof with iron group metals or platinum group metals with platinum group metals
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- 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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a super crystal cell with high catalytic activity, which belongs to the technical field of nano material preparation, and is composed of Pd, Ni, P and Si, wherein the structure of the super crystal cell is a monoclinic structure, and the Pd, Si, Ni and P in the super crystal cell are alternately arranged and are in a super-ordered structure in atom arrangement and element distribution. The super cell size is 1.0-1.8 nm. The ordered structure of the super unit cell enables the surface hydrogen evolution overpotential to be as low as 50 mV. The invention also discloses a preparation method of the composition. The super crystal cell with high catalytic activity has good catalytic effect on hydrogen production by water electrolysis, and the overpotential of hydrogen evolution on the surface can be as low as 50 mV. The preparation method of the super crystal cell with high catalytic activity has simple preparation process and does not need complex processes such as hydrothermal process, precipitation and the like.
Description
Technical Field
The invention belongs to the technical field of nano material preparation, and particularly relates to a super crystal cell with high catalytic activity and a preparation method thereof.
Background
The hydrolysis hydrogen production has the characteristics of rapidness and cleanness, and is an important acquisition mode of hydrogen energy in the future.
But the hydrogen evolution reaction can only be generated at a very negative potential. In order to shift the potential in the forward direction, a catalyst is often used.
At present, the catalyst with the most positive surface hydrogen evolution potential is a Pt-based nanocatalyst. However, Pt is a rare metal and expensive.
Disclosure of Invention
The purpose of the invention is as follows: the invention provides a super crystal cell with high catalytic activity, and the super-large ordered crystal cell has good catalytic effect on hydrogen production by water electrolysis; the invention also aims to provide a preparation method thereof, aiming at preparing a high-efficiency hydrolysis hydrogen production catalyst by using the abundant Pd metal derivative.
The technical scheme is as follows: in order to achieve the purpose, the invention adopts the following technical scheme:
a super crystal cell with high catalytic activity is composed of Pd, Ni, P and Si, and has a monoclinic structure, wherein the Pd, Si, Ni and P are alternately arranged in the super crystal cell and are in a super-ordered structure in atomic arrangement and element distribution.
Furthermore, the size of the super unit cell is 1.0-1.8 nm.
Furthermore, the ordered structure of the super unit cell enables the surface hydrogen evolution potential to be as low as 50 mV.
Further, a preparation method of the super unit cell with high catalytic activity is obtained by keeping the temperature of the amorphous Ni-Pd-P-Si-B below the crystallization starting temperature in the protective atmosphere.
Further, the amorphous component of Ni-Pd-P-Si-B is as follows: 15-45 at% of Pd, 35-65 at% of Ni, 12-16 at% of P, 1-3 at% of Si and 3-5 at% of B.
Further, the temperature of the heat preservation is 20-60 ℃, and the heat preservation time is 2-10 hours.
Has the advantages that: compared with the prior art, the super unit cell with high catalytic activity has good catalytic effect on hydrogen production by water electrolysis, and the overpotential of hydrogen evolution on the surface can be as low as 50 mV. The preparation method of the super crystal cell with high catalytic activity has simple preparation process and does not need complex processes such as hydrothermal process, precipitation and the like.
Drawings
FIG. 1 is a diagram of a three-dimensional atom probe with a super-large unit cell formed in a Ni-Pd-P-Si-B crystal;
FIG. 2 is the ordered distribution diagram of Pd (middle) and Ni (lower) in the energy loss spectrum of the NiPdPSi super large unit cell high resolution dark field image (upper).
Detailed Description
The invention is further described with reference to the following figures and specific examples.
A super cell with high catalytic activity is composed of Pd, Ni, P and Si atoms, and the structure of the super cell is a monoclinic structure super cell which is in an ordered arrangement of (Pd, Si) and (Ni, P) atoms in the element arrangement, namely, in a super-ordered structure in both the atom arrangement and the element distribution (as shown in figure 1 and figure 2). The super cell size is 1.0-1.8 nm. The ordered structure of the super unit cell enables the surface hydrogen evolution potential to be as low as 50 mV.
A preparation method of a super unit cell with high catalytic activity is obtained by carrying out heat preservation on Ni-Pd-P-Si-B amorphous crystal below the crystallization starting temperature in a protective atmosphere. The amorphous component of Ni-Pd-P-Si-B is as follows: 15-45 at% of Pd, 35-65 at% of Ni, 12-16 at% of P, 1-3 at% of Si and 3-5 at% of B.
The temperature for heat preservation is 20-60 ℃, and the time for heat preservation is 2-10 hours.
Example 1
And (3) carrying out heat preservation on the Ni-Pd-P-Si-B amorphous alloy for 8 hours at the temperature of 50 ℃ below the crystallization starting temperature in a protective atmosphere. In the amorphous, the content of Pd is 45 at%, the content of Ni is 35 at%, the content of P is 16 at%, the content of Si is 1 at%, and the content of B is 3 at%.
The crystal with the NiPdSiP super crystal cell structure is prepared through the steps, the crystal cell is a monoclinic structure, the size of the crystal cell is 1.8nm, atoms (Pd, Si) and (Ni, P) in the crystal cell are alternately arranged and are in a super-ordered structure in atom arrangement and element distribution, and the specific component distribution and the atom structure distribution are respectively shown in a figure 1 and a figure 2. Water electrolysis is carried out on the surface of the alloy to produce hydrogen, and the overpotential is 50 mV.
Example 2
And (3) carrying out heat preservation on the Ni-Pd-P-Si-B amorphous for 10 hours at the temperature which is 30 ℃ below the crystallization starting temperature in the protective atmosphere. In the amorphous, the content of Pd is 40 at%, the content of Ni is 40 at%, the content of P is 15 at%, the content of Si is 1 at%, and the content of B is 4 at%.
The crystal with the NiPdSiP super crystal cell structure is prepared through the steps, the crystal cell is a monoclinic structure, the size of the crystal cell is 1.6nm, and (Pd, Si) and (Ni, P) in the crystal cell are alternately arranged and are in a super-ordered structure in atomic arrangement and element distribution. The hydrogen is produced on the surface of the alloy by water electrolysis, and the overpotential is 65 mV.
Example 3
And (3) keeping the temperature of the Ni-Pd-P-Si-B amorphous below the crystallization starting temperature of 60 ℃ for 10 hours in a protective atmosphere. The content of Pd in the amorphous is 30 at%, the content of Ni is 50 at%, the content of P is 15 at%, the content of Si is 2 at%, and the content of B is 3 at%.
The crystal with the NiPdSiP super crystal cell structure is prepared through the steps, the crystal cell is a monoclinic structure, the size of the crystal cell is 1.5nm, and (Pd, Si) and (Ni, P) in the crystal cell are alternately arranged and are in a super-ordered structure in atomic arrangement and element distribution. Water electrolysis is carried out on the surface of the alloy to produce hydrogen, and the overpotential is 76 mV.
Example 4
And (3) carrying out heat preservation on the Ni-Pd-P-Si-B amorphous for 5 hours at a temperature which is 30 ℃ below the crystallization starting temperature in a protective atmosphere. In the amorphous, the content of Pd is 20 at%, the content of Ni is 60 at%, the content of P is 14 at%, the content of Si is 2 at%, and the content of B is 4 at%.
The crystal with the NiPdSiP super crystal cell structure is prepared through the steps, the crystal cell is a monoclinic structure, the size of the crystal cell is 1.2nm, and (Pd, Si) and (Ni, P) in the crystal cell are alternately arranged and are in a super-ordered structure in atomic arrangement and element distribution. Hydrogen is produced on the surface of the alloy by water electrolysis, and the overpotential is 85 mV.
Example 5
And (3) carrying out heat preservation on the Ni-Pd-P-Si-B amorphous alloy for 2 hours at the temperature which is 20 ℃ below the crystallization starting temperature in the protective atmosphere. The content of Pd in the amorphous is 15 at%, the content of Ni is 65 at%, the content of P is 12 at%, the content of Si is 3 at%, and the content of B is 5 at%.
The crystal with the NiPdSiP super crystal cell structure is prepared through the steps, the crystal cell is a monoclinic structure, the size of the crystal cell is 1.0nm, and (Pd, Si) and (Ni, P) in the crystal cell are alternately arranged and are in a super-ordered structure in atomic arrangement and element distribution. Water electrolysis is carried out on the surface of the alloy to produce hydrogen, and the overpotential is 93 mV.
The above description is only of the preferred embodiments of the present invention, and it should be noted that: it will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the invention and these are intended to be within the scope of the invention.
Claims (5)
1. A super cell with high catalytic activity, characterized by: the super crystal cell with high catalytic activity consists of Pd, Ni, P and Si, and has a monoclinic structure, wherein the Pd, Si, Ni and P in the super crystal cell are alternately arranged and are in a super-ordered structure in atomic arrangement and element distribution; the crystal cell is obtained by crystallizing Ni-Pd-P-Si-B amorphous in a protective atmosphere at a temperature below the crystallization starting temperature and preserving heat; the heat preservation temperature is 20-60 ℃, and the heat preservation time is 2-10 hours.
2. A highly catalytically active super cell according to claim 1, wherein: the super unit cell size is 1.0-1.8 nm.
3. A highly catalytically active super cell according to claim 1, wherein: the ordered structure of the super unit cell enables the surface hydrogen evolution potential to be as low as 50 mV.
4. A method for preparing a super cell with high catalytic activity according to any of claims 1 to 3, characterized in that: the Ni-Pd-P-Si-B amorphous is obtained after heat preservation below the crystallization starting temperature in a protective atmosphere; the heat preservation temperature is 20-60 ℃, and the heat preservation time is 2-10 hours.
5. The method of claim 4, wherein the super cell has a high catalytic activity, and the method comprises the steps of: the Ni-Pd-P-Si-B amorphous component comprises: 15-45 at% of Pd, 35-65 at% of Ni, 12-16 at% of P, 1-3 at% of Si and 3-5 at% of B.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105734457A (en) * | 2016-02-29 | 2016-07-06 | 天津大学 | Method for preparing Pd-Cu-S amorphous material by using amorphous alloy and application thereof |
| CN109881028A (en) * | 2019-04-11 | 2019-06-14 | 福建工程学院 | A kind of resistant amorphous alloy system and its application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105734457A (en) * | 2016-02-29 | 2016-07-06 | 天津大学 | Method for preparing Pd-Cu-S amorphous material by using amorphous alloy and application thereof |
| CN109881028A (en) * | 2019-04-11 | 2019-06-14 | 福建工程学院 | A kind of resistant amorphous alloy system and its application |
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