CN105734457B - Method for preparing Pd-Cu-S amorphous material by using amorphous alloy and application thereof - Google Patents
Method for preparing Pd-Cu-S amorphous material by using amorphous alloy and application thereof Download PDFInfo
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- CN105734457B CN105734457B CN201610112501.8A CN201610112501A CN105734457B CN 105734457 B CN105734457 B CN 105734457B CN 201610112501 A CN201610112501 A CN 201610112501A CN 105734457 B CN105734457 B CN 105734457B
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- 239000000463 material Substances 0.000 title claims abstract description 22
- 229910000808 amorphous metal alloy Inorganic materials 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims abstract description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 230000035484 reaction time Effects 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910002528 Cu-Pd Inorganic materials 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002178 crystalline material Substances 0.000 claims description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 16
- 229910052763 palladium Inorganic materials 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 238000005868 electrolysis reaction Methods 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 150000002739 metals Chemical class 0.000 claims description 5
- 238000002604 ultrasonography Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 4
- 238000004140 cleaning Methods 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 3
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 21
- 230000003197 catalytic effect Effects 0.000 description 9
- 238000004502 linear sweep voltammetry Methods 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000005300 metallic glass Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/001—Amorphous alloys with Cu as the major constituent
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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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
- B01J27/045—Platinum group metals
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/08—Alloys with open or closed pores
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses a method for preparing a Pd-Cu-S amorphous material by using an amorphous alloy, which comprises the following steps of: the Ti content is 20-30%, the Cu content is 50-65%, and the Pd content is 5-20%; cutting the Ti-Cu-Pd amorphous alloy into strips with the thickness of 10-30 mu m, the width of 15-20 mm and the length of 1-3 cm; ultrasonically treating the strip in absolute ethyl alcohol for 5min, cleaning with deionized water, and drying for later use; the strip and a sulfuric acid aqueous solution with the molar concentration of 10M-15M are placed in a closed container together for reaction, the reaction temperature is 70-110 ℃, the reaction time is 12-36 h, a sample prepared after the reaction is finished is washed and dried to obtain the Pd-Cu-S amorphous material, the specific surface area of the amorphous material is large, the amorphous material has a composite nano porous structure with electrocatalytic activity, the implementation cost is low, the operation is simple and convenient, the time consumption is short, and the synthesis method is efficient and economical.
Description
Technical field
The present invention relates to a kind of novel nano-material, it is mainly used in the production hydrogen catalyst material in water electrolysis system.
Background technology
In recent years, hydrogen energy source Yin Qigao conversion efficiency and cleanliness without any pollution are received more and more in new energy field
Concern.However, the activity and Cost Problems of anode catalyst govern the large-scale application of DMFC always.Pt
And Pt based alloys limit Pt and Pt base catalyst as the electrolysis aquatic products hydrogen catalyst of best performance show, its price and reserves
Commercial applications.Pd and Pt has closely similar chemical property, but it is superior to Pt in terms of price and reserves.In addition, Pd
Base catalyst also shows higher catalytic stability.
Although pure Pd catalyst is with good intrinsic electro catalytic activity, its active site is less so that pure Pd
Catalyst entirety catalytic activity is not high enough.By carrying out vulcanizing treatment to pure Pd, it is catalyzed production hydrogen activity site and turned from Pd atoms
S atom is moved on to, while by preparing amorphous state Pd-S catalyst so that exposed to the S atom increase of material surface, so that significantly
Increase the catalytic active site of material, and then lift the overall catalytic activity of material.In addition, the addition of Cu atoms can improve material
Absorption to hydrogen and release free energy, and improve with this intrinsic catalytic activity of material.Therefore, the appropriate method of selection prepares non-
Brilliant Pd-Cu-S catalyst can lift the catalytic activity of palladium catalyst to greatest extent.
The content of the invention
For prior art, a kind of cost of present invention offer is low, preparation process simply prepares Pd- with amorphous alloy
The method of Cu-S non-crystalline materials, implementation cost of the present invention is low, easy to operate, time-consuming short, is a kind of synthetic method of high-efficiency and economic,
The composite that the present invention is prepared is mainly used in being electrolysed the cathod catalyst in aquatic products hydrogen field.
In order to solve the above-mentioned technical problem, a kind of method that Pd-Cu-S non-crystalline materials are prepared with amorphous alloy of the present invention,
Comprise the following steps：
Step 1: preparing Ti-Cu-Pd non-crystaline amorphous metals according to following components and atom percentage content：Ti content is 20%-
30%, Cu content are 50%-65%, and Pd content is 5%-20%；
Step 2: it is 10 μm -30 μm that Ti-Cu-Pd non-crystaline amorphous metals made from step one are cut into thickness, width is
15mm-20mm, length is 1cm-3cm band；The band in absolute ethyl alcohol after ultrasound 5min, in deionized water cleaning and in
Air drying is standby；
Step 3: by the sulfuric acid water that Ti-Cu-Pd AMORPHOUS ALLOY RIBBONSs made from step 2 and molar concentration are 10M-15M
Solution, which is together placed in closed container, to be reacted, and reaction temperature is 70 DEG C -110 DEG C, and the reaction time is 12h-36h, will be reacted
Obtained sample deionized water rinsing after end, and the Pd-Cu-S with nano-porous structure is obtained after drying in atmosphere
Non-crystalline material.
Compared with prior art, the beneficial effects of the invention are as follows：
It is the preparation method of the most frequently used Pd base catalyst on a support material by the load of Pd nano particles, but Pd particles
It can dissolve and come off in long-range electrocatalytic reaction, therefore the long-range catalytic performance of such catalyst is not high.Use de- alloyage
The nano material of preparation has the nano-porous structure of co-continuous, and such material has high specific surface area, good electric conductivity
And high stability and mass transfer can be promoted, pure palladium is vulcanized in addition, catalytic active site can be effectively improved total
Amount.In addition, the addition of Cu atoms can improve material to the absorption of hydrogen and release free energy, and the intrinsic of material is improved with this urged
Change activity and reduce palladium usage amount, therefore have preferable application prospect in the preparation field of electrolysis aquatic products hydrogen catalyst.Compare
In crystalline alloy, the composition regulation and control of non-crystaline amorphous metal are more flexible, and Elemental redistribution is more uniform, therefore are a kind of preferably de- alloys
Persursor material.The present invention is stable by taking off Pd-Cu-S non-crystalline materials prepared by alloyage, nano-porous structure chemical property,
Its electro-catalysis under overpotential 200mV in linear sweep voltammetry test produces the current density of hydrogen up to 49.37mA/cm2。
Brief description of the drawings
Fig. 1 is the SEM figures of Pd-Cu-S non-crystalline material nano surface loose structures prepared by embodiment 1；
Fig. 2 is the SEM figures of Pd-Cu-S non-crystalline material nano surface loose structures prepared by embodiment 2；
Fig. 3 is the SEM figures of Pd-Cu-S non-crystalline material nano surface loose structures prepared by embodiment 3；
Fig. 4 is the SEM figures of Pd-Cu-S non-crystalline material nano surface loose structures prepared by embodiment 4；
Fig. 5 is that each Pd-Cu-S non-crystalline materials nano surface loose structure linear sweep voltammetry prepared by embodiment 1-4 is bent
Line.
Embodiment
The inventive method is described further with reference to specific embodiment.It is the side for understanding to provide embodiment
Just, it is in no way intended to limit the present invention.
Embodiment 1：A kind of Pd-Cu-S non-crystalline materials with nano-porous structure are prepared, with amorphous alloy and are utilized
Prepared by the de- alloyage of chemistry, its step is as follows：
Step 1: preparing Ti-Cu-Pd non-crystaline amorphous metals according to following components and atom percentage content：Ti content is
The content that 30%, Cu content are 65%, Pd is 5%；
Step 2: by Ti made from step one30Cu65Pd5It is 10 μm -30 μm that non-crystaline amorphous metal, which is cut into thickness, and width is
15mm-20mm, length is 1cm-3cm band；The band in absolute ethyl alcohol after ultrasound 5min, in deionized water cleaning and in
Air drying is standby；
Step 3: taking the Ti as made from step 230Cu65Pd5AMORPHOUS ALLOY RIBBONS quality 0.1g and 46ml molar concentration
Together it is placed in closed container, and is placed in 70 DEG C of drying boxes, insulation reaction 12h for 10M aqueous sulfuric acid, after reaction terminates
Obtained sample deionized water rinsing, is dried in atmosphere, obtains the Pd-Cu-S non-crystalline materials with nano-porous structure.
Fig. 1 shows the SEM figures of the nano-porous structure of Pd-Cu-S non-crystalline materials made from the embodiment 1.The composite wood
Material has high specific surface area, good electric conductivity and high stability and can promote mass transfer, therefore in electrolysis water
The preparation field of production hydrogen catalyst has preferable application prospect.Compared to crystalline alloy, the composition regulation and control of non-crystaline amorphous metal are more
Flexibly, Elemental redistribution is more uniform, therefore is a kind of preferably de- alloy persursor material.By taking off Pd- prepared by alloyage
Cu-S non-crystalline materials, nano-porous structure chemical property is stable, and the Pd-Cu-S amorphous that embodiment 1 is prepared is shown in Fig. 5
The nano-porous structure linear sweep voltammetry curve of material, its electricity under overpotential 200mV in linear sweep voltammetry test is urged
Change the current density of production hydrogen up to 49.37mA/cm2。
Embodiment 2：
Preparation process is substantially the same manner as Example 1, and it the difference is that only：In step one, Ti content is 30%, Cu
Content be 50%, Pd content be 20%；In step 3, the molar concentration of aqueous sulfuric acid is 13M, and reaction temperature is 110
DEG C, the reaction time is 24h.Fig. 2 shows the SEM of the nano-porous structure of Pd-Cu-S non-crystalline materials made from the embodiment 2
Figure, Fig. 5 shows the nano-porous structure linear sweep voltammetry curve for the Pd-Cu-S non-crystalline materials that embodiment 2 is prepared, its
Electro-catalysis produces the current density of hydrogen up to 21.90mA/cm under overpotential 300mV in linear sweep voltammetry test2。
Embodiment 3：
Preparation process is substantially the same manner as Example 1, and it the difference is that only：In step one, Ti content is 30%, Cu
Content be 65%, Pd content be 5%；In step 3, the molar concentration of aqueous sulfuric acid is 15M, and reaction temperature is 90 DEG C,
Reaction time is 24h.Fig. 3 shows the SEM figures of the nano-porous structure of Pd-Cu-S non-crystalline materials made from the embodiment 3, figure
5 show the nano-porous structure linear sweep voltammetry curve for the Pd-Cu-S non-crystalline materials that embodiment 3 is prepared, and its is online
Property scanning volt-ampere test under overpotential 124mV electro-catalysis production hydrogen current density up to 49.37mA/cm2。
Embodiment 4：
Preparation process is substantially the same manner as Example 1, and it the difference is that only：In step one, Ti content is 30%, Cu
Content be 65%, Pd content be 5%；In step 3, the molar concentration of aqueous sulfuric acid is 15M, and reaction temperature is 90 DEG C,
Reaction time is 36h.Fig. 4 shows the SEM figures of the nano-porous structure of Pd-Cu-S non-crystalline materials made from the embodiment 4, figure
5 show the nano-porous structure linear sweep voltammetry curve for the Pd-Cu-S non-crystalline materials that embodiment 4 is prepared, and its is online
Property scanning volt-ampere test under overpotential 300mV electro-catalysis production hydrogen current density up to 50.00mA/cm2。
It can be drawn by above-described embodiment, the Pd- with nano-porous structure can be obtained according to preparation method of the present invention
Cu-S non-crystalline materials.The nano-porous structure of the Pd-Cu-S non-crystalline materials is in the linear sweep voltammetry test obvious hydrogen of appearance
Air elutriation goes out electric current, illustrates that the material prepared is good in electrolysis aquatic products hydrogen field application prospect.
Although above in conjunction with accompanying drawing, invention has been described, and the invention is not limited in above-mentioned specific implementation
Mode, above-mentioned embodiment is only schematical, rather than restricted, and one of ordinary skill in the art is at this
Under the enlightenment of invention, without deviating from the spirit of the invention, many variations can also be made, these belong to the present invention's
Within protection.
Claims (6)
1. a kind of method that Pd-Cu-S non-crystalline materials are prepared with amorphous alloy, it is characterised in that comprise the following steps：
Step 1: preparing Ti-Cu-Pd non-crystaline amorphous metals according to following components and atom percentage content：Ti content is 20%-
30%, Cu content are 50%-65%, and Pd content is 5%-20%；
Step 2: Ti-Cu-Pd non-crystaline amorphous metals made from step one are cut into thickness for 10 μm -30 μm, width is 15mm-
20mm, length is 1cm-3cm band；The band after ultrasound 5min, is cleaned and in air in absolute ethyl alcohol in deionized water
Middle drying for standby；
Step 3: by the aqueous sulfuric acid that Ti-Cu-Pd AMORPHOUS ALLOY RIBBONSs made from step 2 and molar concentration are 10M-15M
Together it is placed in closed container and is reacted, reaction temperature is 70 DEG C -110 DEG C, and the reaction time is 12h-36h, and reaction is terminated
Obtained sample deionized water rinsing afterwards, and after drying in atmosphere, obtain the Pd-Cu-S amorphous with nano-porous structure
Material.
2. the method for Pd-Cu-S non-crystalline materials is prepared with amorphous alloy according to claim 1, wherein,
In step one, the content that the content that Ti content is 30%, Cu is 65%, Pd is 5%；
In step 3, the molar concentration of aqueous sulfuric acid is 10M, and reaction temperature is 70 DEG C, and the reaction time is 12h.
3. the method for Pd-Cu-S non-crystalline materials is prepared with amorphous alloy according to claim 1, wherein,
In step one, the content that the content that Ti content is 30%, Cu is 50%, Pd is 20%；
In step 3, the molar concentration of aqueous sulfuric acid is 13M, and reaction temperature is 110 DEG C, and the reaction time is 24h.
4. the method for Pd-Cu-S non-crystalline materials is prepared with amorphous alloy according to claim 1, wherein,
In step one, the content that the content that Ti content is 30%, Cu is 65%, Pd is 5%；
In step 3, the molar concentration of aqueous sulfuric acid is 15M, and reaction temperature is 90 DEG C, and the reaction time is 24h.
5. the method for Pd-Cu-S non-crystalline materials is prepared with amorphous alloy according to claim 1, wherein,
In step one, the content that the content that Ti content is 30%, Cu is 65%, Pd is 5%；
In step 3, the molar concentration of aqueous sulfuric acid is 15M, and reaction temperature is 90 DEG C, and the reaction time is 36h.
6. a kind of method system for preparing Pd-Cu-S non-crystalline materials with amorphous alloy according to any one of claim 1 to 5
Application of the standby obtained Pd-Cu-S non-crystalline materials in electrolysis aquatic products hydrogen catalyst material.
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| CN108786853A (en) * | 2018-06-13 | 2018-11-13 | 天津大学 | Nano-porous catalyst method, nanoporous PdCuNi-S catalyst and purposes are prepared using crystal alloy |
| CN110923737A (en) * | 2018-09-20 | 2020-03-27 | 天津大学 | Nano porous hydrogen production catalyst and preparation method thereof |
| CN112342567B (en) * | 2019-08-09 | 2022-02-22 | 天津大学 | Al-Ti-Ni crystal-amorphous composite material prepared from aluminum-based alloy and preparation method and application thereof |
| CN111318720B (en) * | 2020-03-04 | 2022-10-25 | 王冲 | Cubic PtCoS alloy nano-particles and preparation method thereof |
| CN111804316B (en) * | 2020-06-22 | 2022-03-11 | 东南大学 | Super crystal cell with high catalytic activity and preparation method thereof |
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| CN103055891A (en) * | 2012-12-03 | 2013-04-24 | 天津大学 | Method for preparing nano porous titanium dioxide thin film doped with Pd by constant voltage dealloying method on amorphous alloy stripe |
| CN104475125A (en) * | 2014-11-06 | 2015-04-01 | 天津大学 | Method for preparing Pd/CuO composite nanometer porous material by using amorphous alloy for dealloying |
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