CN114457365A - Pt-Ni composite material, preparation method thereof and application thereof as catalyst for hydrogen production by electrolyzing water - Google Patents
Pt-Ni composite material, preparation method thereof and application thereof as catalyst for hydrogen production by electrolyzing water Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 62
- 229910002845 Pt–Ni Inorganic materials 0.000 title claims abstract description 58
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 34
- 239000001257 hydrogen Substances 0.000 title claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000003054 catalyst Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 77
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 63
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 31
- 239000000758 substrate Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 15
- 150000002500 ions Chemical class 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
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- 238000011534 incubation Methods 0.000 claims description 6
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- 239000003960 organic solvent Substances 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 5
- 229910002621 H2PtCl6 Inorganic materials 0.000 claims description 3
- 229910020437 K2PtCl6 Inorganic materials 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 29
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910000474 mercury oxide Inorganic materials 0.000 description 2
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 2
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- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 1
- 229910018493 Ni—K Inorganic materials 0.000 description 1
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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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/061—Metal or alloy
-
- 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
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/081—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the element being a noble metal
-
- 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
Abstract
The invention discloses a Pt-Ni composite material, a preparation method thereof and application thereof as a catalyst for hydrogen production by water electrolysis, belonging to the technical field of catalysts for hydrogen production by water electrolysis, and the invention can realize the high-efficiency and low-cost preparation of the Pt-Ni composite material by one-step replacement reaction: the method comprises the following steps of (1) reducing Pt ions into a metal simple substance through spontaneous replacement reaction at room temperature by taking a nickel-based material as a substrate, and firmly attaching the metal simple substance to the substrate material to form a three-dimensional composite material with a self-supporting structure, wherein the three-dimensional composite material can be directly used as an electrode to catalyze and electrolyze water to prepare hydrogen; the synthesis method of the Pt-Ni composite material is simple, flexible and short in period, almost has no requirement on equipment, is not limited by synthesis places/containers, has very low Pt dosage, greatly saves the preparation cost of the material, has catalytic hydrogen evolution activity far superior to that of a commercial Pt/C material under an alkaline condition, and lays a solid foundation for realizing efficient large-scale industrial hydrogen preparation by electrolyzing water.
Description
Technical Field
The invention relates to the technical field of catalysts for hydrogen production by water electrolysis, in particular to a Pt-Ni composite material, a preparation method thereof and application thereof as a catalyst for hydrogen production by water electrolysis.
Background
Hydrogen energy has the advantages of high energy density, recyclability, no carbon emission and the like, and is thus praised as an ideal future energy carrier. Although the hydrogen production method is diversified, the method for preparing hydrogen by electrolyzing water has important and very important application prospect, mainly because the electrolyzed water has the advantages of abundant raw materials, environmental protection, strong operability and the like. Due to the fact that the acidic electrolyte has the factors of corrosion on equipment, lack of a high-activity electrocatalyst in an anode of the acidic solution and the like, large-scale hydrogen generation is expected to be achieved by using the alkaline or neutral solution. Currently, the efficiency of hydrogen generation from alkaline water is about 30-40%, while the neutral solution efficiency is lower. In view of this, the development of an electrode material with high activity is one of effective strategies for improving the hydrogen production efficiency of water electrolysis and reducing the energy consumption of industrial water electrolysis.
Currently, although numerous studies have confirmed that non-noble metal electrocatalysts have good performance in catalyzing electrolysis of water, the advantages of Pt-based catalytic materials in practical applications are irreplaceable. In order to reduce the cost and further improve the performance-cost ratio, it is of great practical significance to develop Pt-based electrocatalysts in various forms. Common Pt-based electrocatalyst optimization methods can be largely divided into two categories: one is to expose more catalytic sites by maximizing the specific surface area of the catalyst, such as synthesizing a monatomic Pt catalyst. Another common strategy is to modulate the intrinsic activity of the catalytic site at the atomic level, e.g. chemical doping. Based on the above strategy, constructing a self-supporting three-dimensional heterojunction platinum-based catalyst is a very effective method, which can simultaneously increase the intrinsic activity of active sites while increasing the number of active sites per unit area.
Theoretical calculations have demonstrated that Pt catalytic sites do not cleave HO-H bonds well during water splitting. Therefore, it has proven feasible to modulate the catalytic activity of Pt sites with transition metal oxides. That is, the transition metal oxide can accelerate the decomposition of water, and the Pt sites can provide catalytic sites for the adsorption and subsequent recombination of atomic hydrogen. For example, the Markovic group found that ultra-thin Ni (OH) was utilized as compared to Pt single crystals2The activity of the modified Pt (111) composite material is increased by 8 times. To further improve the catalytic activity of platinum-based multi-phase catalysts, the Zhao topic group synthesizes NiO/PtNi nanoparticles (PtNi-O/C) with abundant atomic dimensions on a carbon substrate. At an overpotential of 70 mV, PtNi-O/C showed a high quality activity of 7.23 mA/μ g. Although the catalytic materials reported in these documents all exhibit superior propertiesThe preparation method of the catalyst is very tedious and time-consuming, has specific requirements on reaction equipment, and the involved reaction equipment is expensive, which undoubtedly increases the equipment investment, time cost and labor cost of industrial production.
Similarly, most of the current patents relating to the field of electrode materials for hydrogen production by water electrolysis only pay attention to the activity improvement of catalytic materials, and do not consider the cost problem in the material preparation process. For example, chinese patent application CN201910444423.5 discloses a Pt-Ni composite material containing V element as a catalyst for hydrogen production by water electrolysis, and chinese patent application CN202010368208.4 discloses a Pt-Ni-silicate nanotube-graphene composite material as a catalyst for hydrogen production by water electrolysis. The electrode materials disclosed in these patents all require cumbersome synthesis steps, which also result in additional operating costs; in addition, the synthesized platinum-based material needs to be adhered to the surface of a conductive material to form an electrode in a practical application process by using a high molecular polymer, and the active coating of the electrode formed by a later assembly mode can fall off from the conductive substrate in an electrolytic process, so that the stability of the electrode can not be ensured.
Therefore, continuous optimization of the structure of Pt-metal (hydr) oxide is essential for its practical application. Firstly, developing a simpler, low-cost and time-saving synthesis method is crucial to the industrial application of the platinum-transition metal-based catalyst; secondly, the catalyst structure is reasonably designed, and the method has great significance for further improving the long-term durability, catalytic activity and use stability of the catalytic activity.
Disclosure of Invention
An object of the present invention is to provide a method for preparing a Pt — Ni composite material, so as to solve the above problems.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a preparation method of a Pt-Ni composite material comprises the following steps:
(1) taking a nickel-based material as a substrate;
(2) taking a Pt ion-containing aqueous solution as a reaction solution;
(3) and (3) immersing the nickel substrate into a reaction solution containing Pt ions, and standing for reaction for a period of time to obtain the Pt-Ni composite material.
The present invention utilizes the classical spontaneous displacement reaction, i.e. by
The simple chemical reaction can synthesize the Pt-Ni composite material in one step.
According to the invention, Pt ions are reduced into a metal simple substance and firmly attached to a substrate material through a one-step replacement reaction and a spontaneous replacement reaction at room temperature by taking a nickel-based material as the substrate, so as to form the three-dimensional composite material with a stable structure.
In addition, because Pt atoms in the Pt-Ni composite material are anchored to a nickel substrate in situ, the nickel substrate can be commercial foam nickel, nickel sheets and the like with a three-dimensional skeleton with a self-supporting structure, so the Pt-Ni composite material can be directly used as an electrode without the need of high molecular polymers for assisting in adhering to the surface of a conductive material to form the electrode for electrocatalytic water decomposition, the problem that an active coating of the electrode formed in a later-stage assembly mode can fall off from the conductive substrate in an electrolysis process in the prior art is solved, and the stability of the electrode is ensured.
As a preferred technical scheme, the nickel substrate in the step (1) is selected from commercial foamed nickel, nickel metal sheets, nickel foils or elementary nickel which is partially or completely converted from nickel compounds. I.e., the nickel base material used in the present invention, includes, but is not limited to, the above-mentioned species.
Preferably, the nickel substrate in step (1) is washed by soaking in an organic solvent and/or an inorganic acid.
That is, if the metallic nickel substrate is newly prepared or the surface is not oxidized, it may not be washed, and if it is not newly prepared or the surface is oxidized, it is preferably first subjected to immersion washing using an organic solvent and an inorganic acid. The organic solvent is mainly used for cleaning grease or other organic residues on the surface of the commercial nickel-based material, and the inorganic acid is used for removing oxides on the surface of the nickel-based material to expose simple nickel so as to reduce platinum atoms in the replacement reaction.
As a further preferred technical solution, the organic solvent is selected from ethanol or acetone; the inorganic acid is selected from hydrochloric acid or nitric acid. The cleaning reagent is easy to mix with water, so that the nickel substrate can be better cleaned; in addition, the price of the solvents is relatively low, and the cost can be effectively reduced.
Preferably, in the step (2), the platinum reagent used for preparing the aqueous solution of Pt ions is selected from H which is easily soluble in water2PtCl6·6H2O or K2PtCl6。
It should be noted that the preparation concentration of the Pt ion aqueous solution is not strictly limited, and the amount of the Pt ion aqueous solution is also not strictly limited, but it is preferable to achieve a low concentration of Pt ions and a high catalytic activity, thereby reducing the cost better.
Preferably, in step (3), the incubation temperature is room temperature.
That is, the incubation temperature is not strictly limited, but room temperature is preferred because the synthesis method is a spontaneous chemical displacement reaction and is not sensitive to temperature, the temperature control does not greatly affect the improvement of the reaction rate, and the temperature control can increase the investment and operation cost of equipment.
Preferably, in step (3), the incubation time is 2 hours.
That is, the present invention is not strictly limited with respect to the incubation time, but is preferably 2 hours, and an appropriate reaction time period ensures complete substitution of platinum in an aqueous solution onto the nickel substrate, while the nickel surface, which is not occupied by platinum, is spontaneously and completely oxidized, thereby forming Pt-NiO having higher activity than the Pt-Ni interface sitesxA catalytic site; however, excessive extension of the reaction time not only increases the time consumption for preparing the material, but also does not contribute much to the improvement of the activity of the material.
The second objective of the present invention is to provide a Pt-Ni composite material prepared by the above method.
The third purpose of the invention is to provide an application of the Pt-Ni composite material prepared by the method as a catalyst for hydrogen production by water electrolysis.
As a preferred technical scheme, the catalyst is used as a cathode or an anode to catalyze pure water or aqueous solution with different pH conditions to produce hydrogen through electrolysis
Compared with the prior art, the invention has the advantages that: the invention adopts simple chemical reaction to synthesize the Pt-Ni composite material in one step, the synthesis method is simple and flexible, the period is short, the requirement on equipment is almost eliminated, the synthesis place/container is not limited, the Pt consumption is very low, and the preparation cost of the material can be effectively saved. The catalytic hydrogen evolution activity of the Pt-Ni composite material under alkaline conditions is far better than that of a commercial Pt/C material, and the current density of the Pt-Ni composite material under the overpotential of 200 mV in a specific embodiment is as high as 183 mA/cm2And is 1.8 times of the performance of the Pt/C material under the same voltage. In addition, the Pt-Ni composite material with the self-supporting structure is at 50 mA/cm2The catalyst can maintain high catalytic activity for at least 100 hours when tested in constant current stability. The Pt-Ni composite material has high and excellent catalytic activity and stability, and lays a solid foundation for realizing efficient large-scale preparation of hydrogen.
Drawings
FIG. 1 is a diagram of an embodiment of a Pt-Ni composite material prepared in example 1 of the present invention;
FIG. 2 shows the use of different volumes of 20 mmol/L H in example 1 of the present invention2PtCl6·6H2X-ray diffraction pattern of Pt-Ni composite prepared from O solution;
FIG. 3 is a scanning electron micrograph of a Pt-Ni composite material prepared in example 1 of the present invention;
FIG. 4 is an energy dispersive X-ray analysis and corresponding elemental proportions for Pt-Ni composites prepared in example 1 of the present invention;
FIG. 5 is an X-ray photoelectron spectrum of the Pt 4f region of the Pt-Ni composite material prepared in example 1 of the present invention;
FIG. 6 is an X-ray photoelectron spectrum of the Ni 2p region of the Pt-Ni composite material prepared in example 1 of the present invention;
FIG. 7 is a comparison of the alkaline catalytic hydrogen evolution activity of Pt-Ni composites prepared in accordance with example 1 of the present invention and other control samples;
FIG. 8 is the catalytic activity of alkaline catalyzed hydrogen evolution for Pt-Ni composites prepared in example 1 of the present invention;
FIG. 9 shows the stability of alkaline catalytic hydrogen evolution of Pt-Ni composite materials prepared in example 1 of the present invention.
Detailed Description
The invention will be further explained with reference to the drawings.
Example 1:
a Pt-Ni composite material is prepared by the following steps:
(1) cleaning treatment: shearing a commercial nickel foam (NiF) with the thickness of 1 cm multiplied by 2 cm, and respectively soaking the commercial nickel foam (NiF) with ethanol and concentrated hydrochloric acid for 10 minutes;
(2) the treated NiF was immersed in a centrifuge tube containing 20 mL of ultrapure water, while 50 mL of 20 mmol/L H was added2PtCl6·6H2And incubating the solution for 2 hours at room temperature to obtain the Pt-Ni composite material.
The photo of the material obtained in this example is shown in the right diagram of fig. 1, in fig. 1, the left diagram is pure nickel foam without Pt loading, and it can be seen from the comparison of fig. 1 that the Pt — Ni composite material prepared in this example is black in appearance;
the X-ray diffraction pattern of the Pt-Ni composite material prepared in this example is shown in FIG. 2, and in FIG. 2, the sample prepared in this example is shown to be at 50 mL of 20 mmol/L H2PtCl6·6H2No Pt content was detected in the case of O; however, the Pt content was increased to 2mL of 20 mmol/L H2PtCl6·6H2Pt was detected at O, indicating that when 50 mL of 20 mmol/L H was used2PtCl6·6H2The Pt atoms in the composite material obtained by O are possibly attached to the Ni substrate in a form of near monoatomic dispersion, and the attaching mode is favorable for realizing the maximum utilization of Pt.
The scanning electron microscope image of the Pt-Ni composite material prepared in this example is shown in fig. 3, and fig. 3 shows that no agglomerated particles appear on the surface of the nickel foam, further confirming that Pt is relatively uniformly attached to the Ni substrate;
the energy dispersive X-ray analysis and corresponding element ratio of the Pt-Ni composite material prepared in this example are shown in FIG. 4, and FIG. 4 shows that the Pt content is only 4.27wt%, which indicates that the manufacturing cost of the Pt-Ni composite material is very low;
the X-ray photoelectron spectra f of Pt 4d and Ni 2p in the Pt-Ni composite material prepared in this example are shown in fig. 5 and fig. 6, respectively, and the corresponding peaks of Pt 4d and Ni 2p in the Pt-Ni composite material are significantly shifted compared with pure Pt and NiF, indicating that Pt and Ni in the Pt-Ni composite material have strong interaction, and the interaction between the different components is beneficial to synergistically improving the catalytic activity of the material.
Example 2:
a Pt-Ni composite material is prepared by the following steps:
(1) cleaning treatment: shearing a NiF block with the size of 1 cm multiplied by 2 cm, firstly carrying out ultrasonic treatment on the NiF block for 10 minutes by using acetone, washing the NiF block with water and alcohol, and then soaking the NiF block for 8 minutes by using concentrated nitric acid;
(2) the treated NiF was immersed in a centrifuge tube containing 20 mL of ultrapure water, while 50 mL of 20 mmol/L H was added2PtCl6·6H2And incubating the solution for 2 hours at 40 ℃ in an O solution to obtain the Pt-Ni composite material.
Example 3:
a Pt-Ni composite material is prepared by the following steps:
(1) cleaning treatment: shearing a NiF block with the size of 1 cm multiplied by 2 cm, and respectively soaking the NiF block with ethanol and concentrated hydrochloric acid for 10 minutes;
(2) the treated NiF was immersed in a centrifuge tube containing 20 mL of ultrapure water, while 50 mL of 20 mmol/L K was added2PtCl6And incubating the solution at room temperature for 2 hours to obtain the Pt-Ni composite material.
Application examples
The Pt-Ni composite material prepared in example 1 above was used as an electrode material for the catalytic electrolysis of water.
A1.0M KOH aqueous solution is used as electrolyte, a carbon rod is used as a counter electrode, mercury/mercury oxide is used as a reference electrode, and a Pt-Ni composite material hydrogen evolution performance test is carried out on a Shanghai Chenghua electrochemical workstation.
The preparation method of the commercial Pt/C electrode is as follows: dispersing 5 mg Pt/C in 490 mL, 500 mL deionized water, 10 mL5% naphthol solution, ultrasonic treating for 1 hr, and dripping 30 mLPt/C solution to surface area of 0.5 x 0.5 cm2After being dried, the carbon surface is directly used as an electrode to test the catalytic hydrogen evolution activity of Pt/C.
Linear Sweep Voltammetry (LSV) tests at a sweep rate of 5 mV/s and a voltage in the range of 0-1V (relative to mercury/mercury oxide as a reference electrode). The constant current stability test has the test current of 50 mA/cm2(current density j = current/electrode area). The electrochemical hydrogen evolution overpotentials referred to in the present invention are all relative to standard hydrogen electrodes.
The catalytic activity of the Pt-Ni composite prepared in example 1 is shown in fig. 7, from which it is clear that the alkaline hydrogen evolution activity of the Pt-Ni composite is significantly superior to commercial Pt/C and commercial NiF throughout the test interval.
Specifically, the method comprises the following steps: the current density is as high as 183 mA/cm under the overpotential of 200 mV21.8 times the performance of the Pt/C material at the same voltage and 12 times the performance of the commercial NiF.
After adjusting the synthesis temperature (example 2) or changing the kind of the Pt precursor (example 3), the synthesized Pt-Ni composite material still has very excellent catalytic activity. As shown in FIG. 8, a Pt-Ni composite material (Pt-Ni-40) synthesized at 40 ℃ and K2PtCl6Synthetic Pt-Ni composite (Pt-Ni-K) as Pt source2PtCl6) The current density reaches 201 mA/cm respectively under the overpotential of 200 mV2And 171 mA/cm2These catalytic activities are superior to commercial Pt/C.
The catalytic stability of the Pt-Ni composite material prepared in example 1 is shown in FIG. 9, from which it is clear that the constant voltage is 50 mA/cm2After the lower Pt-Ni composite material is subjected to a continuous 100-hour stability test, the voltage is only attenuated by 44 mV, which indicates that the Pt-Ni composite material has excellent activity stability.
This patentThe invention is compared with V in the published invention patent CN2019104444232O3The Pt @ Ni-SNT/graphene in NiPt and CN202010368208 has obvious advantages in material preparation and catalytic activity, and particularly:
(1) in the aspect of material preparation: the preparation method is simpler (only 2 hours are needed for synthesizing materials by a one-step method), and the preparation cost is lower (room temperature synthesis is needed, extra equipment is not needed for temperature control, the Pt content is only 4.27wt%, and no equipment is needed except for a reaction vessel);
(2) the application aspect of the catalytic hydrogen evolution activity is as follows: the Pt-Ni composite material has a self-supporting structure, so the Pt-Ni composite material can stably run for a long time under high current density, and the long-term stable operation under the high current density is also an important judgment standard for judging whether the hydrogen evolution material can be really used for actual production.
The above description is intended to be illustrative of the preferred embodiment of the present invention and should not be taken as limiting the invention, but rather, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Claims (10)
1. A preparation method of a Pt-Ni composite material is characterized by comprising the following steps:
(1) taking a nickel-based material as a substrate;
(2) taking a Pt ion-containing aqueous solution as a reaction solution;
(3) and (3) immersing the nickel substrate into a reaction solution containing Pt ions, and standing for reaction to obtain the Pt-Ni composite material.
2. The method of claim 1, wherein the nickel substrate of step (1) is selected from commercial nickel foam, nickel metal flakes, nickel foil, or elemental nickel partially or fully converted from a compound of nickel.
3. The method according to claim 1, wherein the nickel substrate of step (1) is washed by separately soaking with an organic solvent and/or an inorganic acid.
4. The method according to claim 3, wherein the organic solvent is selected from ethanol or acetone; the inorganic acid is selected from hydrochloric acid or nitric acid.
5. The method according to claim 1, wherein in the step (2), the platinum reagent used for preparing the aqueous solution of Pt ions is selected from H2PtCl6·6H2O or K2PtCl6。
6. The method according to claim 1, wherein in the step (3), the incubation temperature is room temperature.
7. The method according to claim 1, wherein in step (3), the incubation time is 2 hours.
8. A Pt-Ni composite material produced by the method of any one of claims 1 to 7.
9. Use of the Pt-Ni composite material prepared by the method of any one of claims 1 to 7 as a catalyst for hydrogen production by electrolysis of water.
10. Use according to claim 9, characterized in that as cathode to catalyze the electrolytic production of hydrogen from pure water or aqueous solutions at different pH conditions.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115928122A (en) * | 2022-11-16 | 2023-04-07 | 成都理工大学 | Nickel phosphide electrocatalytic material and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1785509A (en) * | 2005-11-11 | 2006-06-14 | 中山大学 | Platinum carried foamed nickel catalytic material, its preparation method and application |
| CN108043423A (en) * | 2017-12-19 | 2018-05-18 | 沈阳理工大学 | A kind of method for preparing platinum-nickel alloy catalyst |
| CN113363510A (en) * | 2021-06-02 | 2021-09-07 | 中国科学技术大学 | Hydrogen oxidation and reduction dual-function catalytic electrode and preparation method thereof |
| CN113913858A (en) * | 2021-10-25 | 2022-01-11 | 天津大学 | Preparation method for preparing catalytic electrode rich in crystal defects by liquid nitrogen environment pulse laser direct writing |
| CN113943949A (en) * | 2021-10-21 | 2022-01-18 | 南京林业大学 | Platinum edge-modified nickel-based nano material and preparation method and application thereof |
| US20220235477A1 (en) * | 2020-01-09 | 2022-07-28 | Lg Chem, Ltd. | Electrode for Electrolysis |
-
2022
- 2022-01-20 CN CN202210063520.1A patent/CN114457365B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1785509A (en) * | 2005-11-11 | 2006-06-14 | 中山大学 | Platinum carried foamed nickel catalytic material, its preparation method and application |
| CN108043423A (en) * | 2017-12-19 | 2018-05-18 | 沈阳理工大学 | A kind of method for preparing platinum-nickel alloy catalyst |
| US20220235477A1 (en) * | 2020-01-09 | 2022-07-28 | Lg Chem, Ltd. | Electrode for Electrolysis |
| CN113363510A (en) * | 2021-06-02 | 2021-09-07 | 中国科学技术大学 | Hydrogen oxidation and reduction dual-function catalytic electrode and preparation method thereof |
| CN113943949A (en) * | 2021-10-21 | 2022-01-18 | 南京林业大学 | Platinum edge-modified nickel-based nano material and preparation method and application thereof |
| CN113913858A (en) * | 2021-10-25 | 2022-01-11 | 天津大学 | Preparation method for preparing catalytic electrode rich in crystal defects by liquid nitrogen environment pulse laser direct writing |
Non-Patent Citations (8)
| Title |
|---|
| LEI WANG等: "Platinum-nickel hydroxide nanocomposites for electrocatalytic reduction of water", 《NANO ENERGY》, vol. 31, pages 456 - 461 * |
| 卢世刚,李群,刘庆国,路春,党兵,杨汉西: "氢气在贮氢合金电极上析出反应机理的研究", no. 03 * |
| 周行;肖雷;杨小芳;张书飞;王庆飞;崔荣静;: "基于纳米多孔镍铂与石墨烯复合材料构建的电化学传感器对多巴胺的检测", no. 04, pages 491 - 496 * |
| 彭文屹;朱峰;邓晓华;陶钧;周颖钰;: "电沉积工艺参数对镍-钼-锌三元合金电极析氢催化性能的影响", no. 01 * |
| 牛淑妍;崔欢欢;: "以泡沫镍为基底的纳米级Pt/NiCo制备及其表征", no. 03 * |
| 王松蕊;林伟;朱月香;谢有畅;陈经广;: "单层分散型Pt/Ni双金属催化剂的制备及其C=C和C=O催化加氢性能", no. 04 * |
| 王永亮;范明保;彭亮;吕逍;: "热处理温度对Pt-Ni合金结构演变及催化性能的影响", no. 06, pages 128 - 131 * |
| 胡安俊;舒朝著;龙剑平;: "锂-空气电池MnO_2和Co_3O_4正极催化剂的研究进展", no. 12 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115928122A (en) * | 2022-11-16 | 2023-04-07 | 成都理工大学 | Nickel phosphide electrocatalytic material and preparation method thereof |
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