CN115852429A - Ni 3 Fe-LDH @ NiCoP/NF heterojunction efficient full-electrolysis hydro-electric catalyst and preparation method and application thereof - Google Patents
Ni 3 Fe-LDH @ NiCoP/NF heterojunction efficient full-electrolysis hydro-electric catalyst and preparation method and application thereof Download PDFInfo
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Abstract
Ni 3 Fe-LDH @ NiCoP/NF heterojunction efficient full-electrolysis hydroelectric catalyst and preparation method and application thereof. The invention belongs to the field of electrolytic water catalytic materials. The invention aims to solve the problem of Ni synthesized by the current hydrothermal method 3 Fe-LDH @ NiCoP/NF heterojunction electrocatalyst is not beneficial to electron transmission, and meanwhile, the preparation process is complex and consumes long time and generates toxic and harmful gases in the phosphating treatment process. The invention firstly uses nickel salt, cobalt salt, phosphite and NH 4 Cl and CH 3 COONa is used as electrolyte, a pretreated nickel-based material is used as a working electrode, and NiCoP-x is grown through constant current deposition; then nickel salt and iron salt are used as electrolytes,ni growth by constant voltage deposition using the above product as working electrode 3 Fe-LDH to obtain Ni 3 Fe-LDH @ NiCoP/NF heterojunction efficient full-electrolysis hydro-electric catalyst.
Description
Technical Field
The invention belongs to the field of electrolytic water catalytic materials, and particularly relates to Ni 3 Fe-LDH @ NiCoP/NF heterojunction efficient full-electrolysis hydro-electric catalyst and preparation method and application thereof.
Background
As the conditions of fossil energy depletion and environmental deterioration become more severe, the development and utilization of renewable energy is imminent. Among the various renewable energy sources, hydrogen energy has the advantages of high energy density, zero greenhouse gas emission, etc., and is considered to be one of the most potential energy sources to replace the traditional fossil fuels. Hydrogen production by electrocatalysis water decomposition is an effective method for realizing large-scale production of high-purity hydrogen, but an anode Oxygen Evolution Reaction (OER) in electrolytic water relates to four-proton coupled electron transfer, has slow kinetics and needs higher overpotential, so that the energy conversion rate is low, and the method is a bottleneck which needs to be broken through urgently in the field of hydrogen production by electrolytic water. Currently, the electrocatalyst with the most efficient OER electrocatalytic performance is RuO 2 And IrO 2 However, its industrial application is severely hampered by high price and scarcity. Therefore, the reasonable design and low consumption are urgent to prepare economical, efficient and durable non-noble metal-based nano materials for OER electrocatalytic reaction.
In recent years, numerous non-noble metal-based OER catalysts have been extensively studied. Among them, the transition metal based catalysts such as Fe, co, ni, etc. which are low in cost and rich in reserves are widely used for the OER catalyst due to their tunable 3d electronic configuration and spin state. The metal hydroxide with excellent oxidation resistance in alkaline electrolyte is widely applied to photoelectrocatalysis, capacitors and the like, and is the best OER candidate catalyst, but the single-component hydroxide is difficult to simultaneously meet the excellent high activity, high conductivity, high specific surface area and strong stability of the high-efficiency catalystQualitative property and the like, and has certain limitation in practical application. The multi-component synergy strategy can enable the catalytic material to exert the strongest electrocatalytic performance. It was found that phosphide is considered as a potential catalytic material for OER, but due to its poor intrinsic activity, further improvement is still needed. Organically combines the two to expose more active sites, so that the overall electrocatalytic performance of the material is greatly optimized, and the industrial production and large-scale application of the material are promoted. Thus, ni 3 Fe-LDH @ NiCoP/NF heterojunction efficient full-electrolysis water-power catalyst application, however, at present, ni 3 The Fe-LDH @ NiCoP/NF heterojunction high-efficiency oxygen evolution electrocatalyst is synthesized by mainly adopting a hydrothermal method, the method is complex in process and long in time consumption, and PH can be generated in the phosphating process 3 Ni prepared by using toxic and harmful gas and hydrothermal-phosphorization-hydrothermal synthesis route 3 Fe-LDH @ NiCoP/NF is generally in the shape of nanowires, and is not favorable for mass transport and electron transport in electrocatalytic reaction.
Disclosure of Invention
The invention aims to solve the problem of Ni synthesized by the current hydrothermal method 3 Fe-LDH @ NiCoP/NF heterojunction electrocatalyst is not beneficial to electron transmission, and the technical problems of complex preparation process, long time consumption and generation of toxic and harmful gases in the phosphating treatment process are solved, so that Ni is provided 3 Fe-LDH @ NiCoP/NF heterojunction efficient full-electrolysis hydro-electric catalyst and preparation method and application thereof.
It is an object of the present invention to provide a Ni alloy 3 The preparation method of the Fe-LDH @ NiCoP/NF heterojunction efficient full-electrolysis hydro-electric catalyst comprises the following steps:
s1: with nickel salts, cobalt salts, phosphites, NH 4 Cl and CH 3 COONa is used as electrolyte, a pretreated nickel-based material is used as a working electrode, niCoP-x is grown in a two-electrode system through constant current deposition, and stirring is continuously carried out in the deposition process;
s2: ni is grown in a three-electrode system by constant-voltage deposition by taking nickel salt and iron salt as electrolytes and taking an S1 product as a working electrode 3 Fe-LDH, stirring continuously in the deposition process to obtain Ni 3 Fe-LDH @ NiCoP/NF heterojunction efficient full-electrolysis hydroelectric catalyst。
Further defined, the nickel salt in S1 comprises NiCl 2 、NiSO 4 、Ni(NO 3 ) 2 ·6H 2 O。
Further defined, the cobalt salt in S1 comprises CoCl 2 、CoSO 4 、Co(NO 3 ) 2 ·6H 2 O。
Further defined, the phosphite in S1 comprises NaH 2 PO 2 、NH 4 H 2 PO 2 、KH 2 PO 2 One or a mixture of several of them according to any ratio.
Further limiting, the concentration of nickel salt in S1 is 0.01-0.1 mol/L, the concentration of cobalt salt is 0.01-0.1 mol/L, the concentration of phosphite is 0.1-0.5 mol/L, NH 4 Cl concentration of 0.1-1.5 mol/L, CH 3 The concentration of COONa is 0.001-0.01 mol/L.
Further defined, the parameters of the constant current deposition in S1 are: the current is 0.05 to 0.5 A.cm -2 The time is 10-60 s and the temperature is 25 ℃.
Further defined, the counter electrode material in S1 is graphite, platinum carbon or titanium sheet.
Further limited, the nickel-based material in S1 is foamed nickel, a nickel sheet or a nickel net.
Further limiting, the pretreatment process in S1: the nickel-based material is sequentially placed in acetone, HCl aqueous solution, ethanol and deionized water for ultrasonic cleaning, and then vacuum drying is carried out.
Further, the nickel salt in S2 comprises nickel sulfate, nickel nitrate, nickel carbonate and nickel phosphate, and the iron salt comprises ferric sulfate and ferric nitrate.
More particularly, the electrolyte in S2 contains at least one nitrate.
Further limiting, the concentration of nickel salt in the electrolyte solution in S2 is 0.1-1.0 mol/L, and the concentration of iron salt is 0.05-0.5 mol/L.
Further, the parameters of constant voltage deposition in S2 are: the voltage is-0.9 to-1.5V, the time is 3 to 30min, and the temperature is 20 to 60 ℃.
Another object of the present invention is to provide a Ni alloy produced by the above method 3 Fe-LThe DH @ NiCoP/NF heterojunction high-efficiency oxygen evolution electrocatalyst is characterized in that the catalyst is in the shape of nanospheres formed by two-dimensional nanosheets, and the nanospheres are communicated with one another through nanofilaments.
It is another object of the present invention to provide Ni prepared by the above method 3 The Fe-LDH @ NiCoP/NF heterojunction efficient full-hydrolysis hydro-electric catalyst is applied as an alkaline full-hydrolysis OER electro-catalyst.
Another object of the present invention is to provide a Ni alloy obtained by the above method 3 The Fe-LDH @ NiCoP/NF heterojunction high-efficiency full-hydrolysis water-electricity catalyst is applied as an alkaline full-hydrolysis HER electrocatalyst.
Compared with the prior art, the invention has the advantages that:
the essential characteristic of the invention is to provide Ni with simple preparation process, low price and excellent performance 3 The preparation method of the Fe-LDH @ NiCoP/NF heterojunction full-hydrolysis hydro-electric catalyst has the following specific advantages:
1) According to the invention, a series of different electrocatalysts are obtained by regulating and controlling the current density in constant-current deposition, so that Ni is enabled to be 3 A unique heterojunction interface is formed between the Fe-LDH and the NiCoP/NF, the microscopic morphology is the nanospheres formed by the two-dimensional nanosheets, and the nanospheres are mutually communicated by the nanowires, so that compared with the nanowires, the morphology can provide good mass transmission and electron transmission channels for catalytic reaction, and the electrocatalytic performance is greatly improved. In addition, the foam metal carrier has strong conductivity, so that electron transfer is accelerated, and the electrochemical active area is increased.
2) The two-step electrodeposition method has short synthesis period and low energy consumption, and is suitable for industrial production.
Drawings
FIG. 1 shows blanks NF, niCoP/NF-0.5 and Ni in example 2 3 Scanning electron micrograph of Fe-LDH-8@ NiCoP/NF-0.5; (a) -blank NF, (b) NiCoP/NF-0.5; (c) Ni 3 Fe-LDH-8@NiCoP/NF-0.5；
FIG. 2 is an XRD pattern of NiCoP/NF-0.5 of example 2;
FIG. 3 LSV plots of water OER for full hydrolysis with electrocatalysts of examples 1-2 and comparative examples 1-2;
FIG. 4 is a Tafel slope plot for the electrocatalyst total water-splitting OERs of examples 1-2 and comparative examples 1-2;
figure 5 LSV plots of fully hydrolyzed HER for the electrocatalysts of examples 3-4 and comparative examples 2-3;
figure 6 is a graph of the Tafel slope of the electrocatalyst total hydrolysis HER of examples 3-4 and comparative examples 2-3;
figure 7 is a plot of the total cell pressure for the electrocatalysts of example 2 and comparative examples 1, 3.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The experimental procedures used in the following examples are conventional unless otherwise specified. The materials, reagents, methods and apparatus used, unless otherwise specified, are conventional in the art and are commercially available to those skilled in the art.
The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," or any other variation thereof, as used in the following embodiments, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
Example 1: ni of the present example 3 The preparation method of the Fe-LDH-8@ NiCoP/NF heterojunction efficient full-electrolysis hydroelectric catalyst comprises the following steps:
S1：
first, niCl containing 0.025mol/L is prepared 2 0.025mol/L of CoCl 2 0.25mol/L of NaH 2 PO 2 1mol/L NH 4 Cl and 0.003mol/L CH 3 Aqueous electrolyte solution of COONa;
then, placing the foamed nickel in acetone for ultrasonic cleaning for 15min, then placing the foamed nickel in 2mol/L HCl aqueous solution for ultrasonic cleaning for 15min, finally sequentially performing ultrasonic cleaning for 10 min by using ethanol and deionized water respectively, and then placing the foamed nickel in a vacuum drying oven for vacuum drying at 60 ℃ until the foamed nickel is completely dried to obtain pretreated foamed nickel;
finally, the pretreated foamed nickel is taken as a working electrode, the titanium sheet electrode is taken as a counter electrode, and the temperature is 25 ℃ and 0.05A cm at room temperature -2 Depositing for 40s under constant current at the current density, continuously stirring in the deposition process, taking out, repeatedly washing for 3 times by using absolute ethyl alcohol and deionized water, and then completely drying in a vacuum oven at 60 ℃;
S2：
first, ni (NO) containing 0.3mol/L was prepared 3 ) 2 ·6H 2 O and 0.1mol/L Fe (NO) 3 ) 3 ·9H 2 An electrolyte aqueous solution of O is used as an electrolyte solution;
then, taking the S1 product as a working electrode, a platinum sheet electrode as a counter electrode and an Ag/AgCl electrode as a reference electrode, carrying out electrochemical deposition for 8min at a constant voltage of-1V at the temperature of 25 ℃, continuously stirring in the deposition process, repeatedly washing for 3 times by using ethanol and deionized water after the deposition is finished, and then drying in a vacuum drying oven at the temperature of 60 ℃ overnight to obtain Ni 3 Fe-LDH-8@ NiCoP/NF heterojunction efficient full-electrolysis hydro-electric catalyst marked as Ni 3 Fe-LDH-8@NiCoP/NF-0.05。
Example 2: ni of the present example 3 The preparation method of the Fe-LDH-8@ NiCoP/NF heterojunction efficient full-electrolysis hydro-electric catalyst comprises the following steps:
S1：
first, niCl containing 0.025mol/L is prepared 2 0.025mol/L of CoCl 2 0.25mol/L NaH 2 PO 2 1mol/L NH 4 Cl and 0.003mol/L CH 3 Aqueous electrolyte solution of COONa;
then, placing the foamed nickel in acetone for ultrasonic cleaning for 15min, then placing the foamed nickel in 2mol/L HCl aqueous solution for ultrasonic cleaning for 15min, finally sequentially performing ultrasonic cleaning for 10 min by using ethanol and deionized water respectively, and then placing the foamed nickel in a vacuum drying oven for vacuum drying at 60 ℃ until the foamed nickel is completely dried to obtain pretreated foamed nickel;
finally, the process is carried out in a batch,the pretreated foamed nickel is used as a working electrode, the titanium sheet electrode is used as a counter electrode, and the temperature is 25 ℃ and 0.5A cm at room temperature -2 Depositing for 40s under constant current at the current density, continuously stirring in the deposition process, taking out, repeatedly washing for 3 times by using absolute ethyl alcohol and deionized water, and then completely drying in a vacuum oven at 60 ℃;
S2：
first, ni (NO) containing 0.3mol/L was prepared 3 ) 2 ·6H 2 O and 0.1mol/L Fe (NO) 3 ) 3 ·9H 2 An electrolyte aqueous solution of O is used as an electrolyte solution;
then, taking the S1 product as a working electrode, a platinum sheet electrode as a counter electrode and an Ag/AgCl electrode as a reference electrode, carrying out electrochemical deposition for 8min at a constant voltage of-1V at the temperature of 25 ℃, continuously stirring in the deposition process, repeatedly washing for 3 times by using ethanol and deionized water after the deposition is finished, and then drying in a vacuum drying oven at the temperature of 60 ℃ overnight to obtain Ni 3 Fe-LDH-8@ NiCoP/NF heterojunction efficient full-electrolysis hydro-electric catalyst marked as Ni 3 Fe-LDH-8@NiCoP/NF-0.5。
Blank NF, S1 products NiCoP/NF-0.5 and Ni in this example 3 The scanning electron microscope picture of Fe-LDH-8@ NiCoP/NF-0.5 is shown in figure 1, and the picture (a) reveals a 3D porous structure of a blank NF substrate, provides rich sites for the growth of a catalyst, has strong self conductivity, is favorable for electron transmission, and accelerates the generation of oxygen evolution reaction; FIG. (b) shows that NiCoP/NF-0.5 consists of nanosheets constituting nanospheres, and nanowires interconnecting the nanospheres, which provides a favorable pathway for mass transport and electron transport; FIG. (c) shows Ni 3 The composite morphology of Fe-LDH-8@ NiCoP/NF-0.5.
The XRD pattern of NiCoP/NF-0.5 in this example is shown in FIG. 2, from which it can be seen that the peak positions are at 40.9 °,45.6 ° and 54.4 °, corresponding to the (111), (210) and (300) crystallographic planes of NiCoP, which is PDF #71-2336. It was confirmed that the electrodeposition method can successfully prepare NiCoP in a very short time.
Example 3: ni of the present example 3 The preparation method of the Fe-LDH-8@ NiCoP/NF heterojunction efficient full-electrolysis hydro-electric catalyst comprises the following steps:
S1：
first, niCl containing 0.025mol/L is prepared 2 0.025mol/L of CoCl 2 0.25mol/L of NaH 2 PO 2 1mol/L NH 4 Cl and 0.003mol/L CH 3 Electrolyte aqueous solution of COONa;
then, placing the foamed nickel in acetone for ultrasonic cleaning for 15min, then placing the foamed nickel in 2mol/L HCl aqueous solution for ultrasonic cleaning for 15min, finally sequentially performing ultrasonic cleaning for 10 min by using ethanol and deionized water respectively, and then placing the foamed nickel in a vacuum drying oven for vacuum drying at 60 ℃ until the foamed nickel is completely dried to obtain pretreated foamed nickel;
finally, the pretreated foamed nickel is taken as a working electrode, the titanium sheet electrode is taken as a counter electrode, and the temperature is 25 ℃ and 0.2A cm at room temperature -2 Depositing for 40s under constant current at the current density, continuously stirring in the deposition process, taking out, repeatedly washing for 3 times by using absolute ethyl alcohol and deionized water, and then completely drying in a vacuum oven at 60 ℃;
S2：
first, ni (NO) was prepared in an amount of 0.3mol/L 3 ) 2 ·6H 2 O and 0.1mol/L Fe (NO) 3 ) 3 ·9H 2 An electrolyte aqueous solution of O is used as an electrolyte solution;
then, taking the S1 product as a working electrode, a platinum sheet electrode as a counter electrode and an Ag/AgCl electrode as a reference electrode, carrying out electrochemical deposition for 8min at a constant voltage of-1V at the temperature of 25 ℃, continuously stirring in the deposition process, repeatedly washing for 3 times by using ethanol and deionized water after the deposition is finished, and then drying in a vacuum drying oven at the temperature of 60 ℃ overnight to obtain Ni 3 Fe-LDH-8@ NiCoP/NF heterojunction efficient full-electrolysis hydro-electric catalyst marked as Ni 3 Fe-LDH-8@NiCoP/NF-0.2。
Example 4: ni of the present example 3 The preparation method of the Fe-LDH-8@ NiCoP/NF heterojunction efficient full-electrolysis hydro-electric catalyst comprises the following steps:
S1：
first, a NiCl solution containing 0.025mol/L was prepared 2 0.025mol/L of CoCl 2 0.25mol/L of NaH 2 PO 2 1mol/L NH 4 Cl and 0.003mol/L CH 3 Aqueous electrolyte solution of COONa;
then, placing the foamed nickel in acetone for ultrasonic cleaning for 15min, then placing the foamed nickel in 2mol/L HCl aqueous solution for ultrasonic cleaning for 15min, finally sequentially performing ultrasonic cleaning for 10 min by using ethanol and deionized water respectively, and then placing the foamed nickel in a vacuum drying oven for vacuum drying at 60 ℃ until the foamed nickel is completely dried to obtain pretreated foamed nickel;
finally, the pretreated foamed nickel is taken as a working electrode, the titanium sheet electrode is taken as a counter electrode, and the temperature is 25 ℃ and 0.4A cm at room temperature -2 Depositing for 40s under constant current at the current density, continuously stirring in the deposition process, taking out, repeatedly washing for 3 times by using absolute ethyl alcohol and deionized water, and then completely drying in a vacuum oven at 60 ℃;
S2：
first, ni (NO) was prepared in an amount of 0.3mol/L 3 ) 2 ·6H 2 O and 0.1mol/L Fe (NO) 3 ) 3 ·9H 2 An electrolyte aqueous solution of O is used as an electrolyte solution;
then, taking the S1 product as a working electrode, a platinum sheet electrode as a counter electrode and an Ag/AgCl electrode as a reference electrode, carrying out electrochemical deposition for 8min at a constant voltage of-1V at the temperature of 25 ℃, continuously stirring in the deposition process, repeatedly washing for 3 times by using ethanol and deionized water after the deposition is finished, and then drying in a vacuum drying oven at the temperature of 60 ℃ overnight to obtain Ni 3 Fe-LDH-8@ NiCoP/NF heterojunction efficient full-electrolysis hydro-electric catalyst marked as Ni 3 Fe-LDH-8@NiCoP/NF-0.4。
Comparative example 1: ruO (RuO) 2 The preparation method of the/NF oxygen evolution electrocatalyst comprises the following steps:
6mg of RuO 2 The powder and 32 microliters of 5wt.% Nafion solution were dissolved in 0.968ml of a water and ethanol mixture, wherein the volume ratio of water to ethanol was 4:1, then carrying out ultrasonic treatment for at least 30min to obtain a uniform mixed solution, then dripping 50 microliters of the mixed solution on foam nickel of 1cm by 1cm, and drying in a vacuum drying oven at 60 ℃ to obtain RuO 2 /NF oxygen evolution electrocatalyst.
Comparative example 2: blank foam nickel as oxygen evolution electrocatalyst
Firstly, placing foamed nickel in acetone for ultrasonic cleaning for 15min, then placing the foamed nickel in 2mol/L HCl aqueous solution for ultrasonic cleaning for 15min, then sequentially using ethanol and deionized water for ultrasonic cleaning for 10 min, and finally placing the foamed nickel in a vacuum drying oven at 60 ℃ until the foamed nickel is completely dried.
Comparative example 3: a preparation method of a Pt/C/NF oxygen evolution electrocatalyst comprises the following steps:
10mg of Pt/C powder and 32. Mu.l of a 5wt.% Nafion solution were dissolved in 0.968ml of a water and ethanol mixture, wherein the volume ratio of water to ethanol was 4:1, performing ultrasonic treatment for at least 30min to obtain a uniform mixed solution, then dripping 50 microliters of the mixed solution on foam nickel of 1cm × 1cm, and drying in a vacuum drying oven at 60 ℃ to obtain the Pt/C/NF oxygen evolution electrocatalyst.
Application example:
the electrocatalysts prepared in examples 1-4 and comparative examples 1-3 were subjected to a full hydrolysis test as the electrocatalysts for OER and HER, the electrolyte being a 1M KOH solution.
And (3) detection test:
the catalyst material is subjected to an electrocatalytic oxygen production (OER) performance test in a standard three-electrode electrolytic cell, wherein the cyclic scanning range is 0.1-1.1V, and the scanning rate is 5mV/s, and the results are shown in Table 1 and figures 3-4. Note that all potentials obtained with the Hg/HgO electrode as a reference electrode in the electrocatalytic test were converted to reversible hydrogen electrode potentials in the property diagrams.
TABLE 1 electrocatalytic oxygen production (OER) performance
| Example 1 | Example 2 | Comparative example 1 | Comparative example 2 | |
| 10mA·cm -2 Overpotential (mV) required for current density | 175 | 126 | 287 | 355 |
| 100mA·cm -2 Overpotential (mV) required for current density | 255 | 182 | 384 | - |
The LSV curves of the electrocatalysts of examples 1-2 and comparative examples 1-2 are shown in FIG. 3, with a current density of 10mA/cm 2 Ni prepared in example 1 3 The overpotential required for Fe-LDH-8@ NiCoP/NF-0.05 was 175mV, ni prepared in example 2 3 The overpotential required for Fe-LDH-8@ NiCoP/NF-0.5 is only 126mV, ruO prepared in comparative example 1 2 The overpotential for/NF was 287mV, and that of blank NF prepared in comparative example 2 was 355mV. It can be seen that the overpotentials of examples 1-2 of the present invention are greatly improved as compared to comparative examples 1-2.
Tafel slope diagrams of the electrocatalysts of examples 1-2 and comparative examples 1-2 are shown in FIG. 4, and Ni obtained in example 1 3 Tafel slope of Fe-LDH-8@ NiCoP/NF-0.05 84.93mV/dec, ni prepared in example 2 3 The Tafel slope of Fe-LDH-8@ NiCoP/NF-0.5 was 36.32mV/dec, ruO made in comparative example 1 2 The Tafel slope for/NF was 83.28mV/dec, and the Tafel slope for the blank NF prepared in comparative example 2 was 87.34mV/dec. The magnitude of the Tafel slope value represents the speed of electron transport kinetics. Therefore, the heterojunction material prepared by the method has high electron transport kinetics.
And secondly, performing an electrocatalytic hydrogen production (HER) performance test on the catalyst material in a standard three-electrode electrolytic cell, wherein the cyclic scanning range is-0.9 to-2V, the scanning rate is 5mV/s, and the result is shown in a figure 5-6.
The LSV curves of the electrocatalysts of examples 3-4 and comparative examples 2-3 are shown in FIG. 5, and it can be seen that the current density is 10mA/cm 2 Ni prepared in example 3 3 The overpotential required for Fe-LDH-8@ NiCoP/NF-0.2 was 165mV, ni prepared in example 4 3 The overpotential required for Fe-LDH-8@ NiCoP/NF-0.4 was only 162mV, the overpotential for Pt/C/NF prepared in comparative example 3 was 151mV, and the overpotential for blank NF prepared in comparative example 2 was 168mV. However, it is worth noting that under high current density, the electrocatalytic performance of the material prepared by the invention is obviously superior to that of a commercial Pt/C catalyst, and when the electrocatalytic performance reaches 200mA/cm 2 At current density of (2), ni obtained in example 3 3 The overpotential required for Fe-LDH-8@ NiCoP/NF-0.2 is 290mV, ni prepared in example 4 3 The overpotential required for Fe-LDH-8@ NiCoP/NF-0.4 is only 283mV, the overpotential for Pt/C/NF prepared in comparative example 3 is 329mV, and the overpotential for blank NF prepared in comparative example 2 is 374mV. The improvement of the electrocatalytic performance is attributed to the fact that Ni 3 Strong coupling between Fe-LDH-8 and NiCoP.
Tafel slope plots for the electrocatalysts of examples 3-4 and comparative examples 2-3 are shown in FIG. 6, and it can be seen that Ni produced in example 3 3 Tafel slope of Fe-LDH-8@ NiCoP/NF-0.2 is 94.63mV/dec, ni from example 4 3 The Tafel slope for Fe-LDH-8@ NiCoP/NF-0.4 was 94.67mV/dec, the Tafel slope for Pt/C/NF prepared in comparative example 3 was 128.86mV/dec, and the Tafel slope for blank NF prepared in comparative example 2 was 157.07mV/dec. The magnitude of the Tafel slope value represents the speed of electron transport kinetics. Therefore, the heterojunction material prepared by the invention has faster electron transport kinetics.
(III) the groove pressure of the catalyst material in the full-hydrolytic reaction is tested, and the result is shown in figure 7.
The total hydrolysis cell pressure diagram of the electrocatalyst of example 2 and comparative examples 1 and 3 is shown in FIG. 7. It can be seen from FIG. 7 that Ni prepared in example 2 3 Fe-LDH-8@ NiCoP/NF-0.5 takes the product as an electrocatalyst of OER and HER to carry out full water splitting at a lower tank pressure of 1.579VCan reach 10mA/cm 2 . As a comparison, ruO prepared in comparative example 1 and comparative example 3 2 the/NF and Pt/C/NF electro-catalysts need 1.732V to reach 10mA/cm 2 The heterojunction material prepared by the method can be used as a high-efficiency full-electrolysis water-electricity catalyst, and provides a great application prospect.
The above description is only a preferred embodiment of the present invention, and these embodiments are based on different implementations of the present invention, and the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.
Claims (10)
1. Ni 3 The preparation method of the Fe-LDH @ NiCoP/NF heterojunction efficient full-electrolysis hydro-electric catalyst comprises the following steps:
s1: with nickel salts, cobalt salts, phosphites, NH 4 Cl and CH 3 COONa is used as electrolyte, a pretreated nickel-based material is used as a working electrode, niCoP-x is grown in a two-electrode system through constant current deposition, and stirring is continuously carried out in the deposition process;
s2: ni is grown by constant voltage deposition in a three-electrode system by taking nickel salt and iron salt as electrolytes and taking an S1 product as a working electrode 3 Fe-LDH, stirring continuously in the deposition process to obtain Ni 3 Fe-LDH @ NiCoP/NF heterojunction efficient full-electrolysis hydroelectric catalyst.
2. The method of claim 1, wherein the nickel salt in S1 comprises NiCl 2 、NiSO 4 、Ni(NO 3 ) 2 ·6H 2 O, cobalt salts including CoCl 2 、CoSO 4 、Co(NO 3 ) 2 ·6H 2 O, phosphites comprising NaH 2 PO 2 、NH 4 H 2 PO 2 、KH 2 PO 2 One or more of the nickel salts, the concentration of the nickel salt is 0.01-0.1 mol-L, the concentration of cobalt salt is 0.01-0.1 mol/L, the concentration of phosphite is 0.1-0.5 mol/L, NH 4 Cl concentration of 0.1-1.5 mol/L, CH 3 The concentration of COONa is 0.001-0.01 mol/L.
3. The method according to claim 1, characterized in that the parameters of galvanostatic deposition in S1 are: the current is 0.05-0.5A cm -2 The time is 10-60 s, the temperature is 25 ℃, and the counter electrode material is graphite, platinum carbon or titanium sheet.
4. The method according to claim 1, wherein the nickel-based material in S1 is foamed nickel, nickel sheet or nickel net, and the pretreatment process comprises the following steps: the nickel-based material is sequentially placed in acetone, HCl aqueous solution, ethanol and deionized water for ultrasonic cleaning, and then vacuum drying is carried out.
5. The method of claim 1, wherein the nickel salt in S2 comprises nickel sulfate, nickel nitrate, nickel carbonate and nickel phosphate, the iron salt comprises ferric sulfate and ferric nitrate, the concentration of the nickel salt in the electrolyte solution is 0.1-1.0 mol/L, and the concentration of the iron salt is 0.05-0.5 mol/L.
6. The method of claim 5, wherein the electrolyte in S2 contains at least one nitrate.
7. The method according to claim 1, wherein the parameters of the constant voltage deposition in S2 are: the voltage is-0.9 to-1.5V, the time is 3 to 30min, and the temperature is 20 to 60 ℃.
8. Ni produced by the method of any one of claims 1 to 7 3 The Fe-LDH @ NiCoP/NF heterojunction efficient full-electrolysis water-electricity catalyst is characterized in that the catalyst is in a nanosphere shape composed of two-dimensional nanosheets, and the nanospheres are mutually communicated through nanofilaments.
9. Ni produced by the method of any one of claims 1 to 7 3 Fe-LDH@NiCThe high-efficiency full-hydrolysis water-electricity catalyst of the oP/NF heterojunction is applied as an alkaline full-hydrolysis water-electricity catalyst (OER).
10. Ni produced by the method of any one of claims 1 to 7 3 The Fe-LDH @ NiCoP/NF heterojunction high-efficiency full-hydrolysis water-electricity catalyst is applied as an alkaline full-hydrolysis HER electrocatalyst.
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