CN115074771B - Nitrogen-doped carbon nanotube-coated Ni 3 ZnC 0.7 Ni heterogeneous nanoparticle electrocatalyst and preparation method thereof - Google Patents

Nitrogen-doped carbon nanotube-coated Ni 3 ZnC 0.7 Ni heterogeneous nanoparticle electrocatalyst and preparation method thereof Download PDF

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CN115074771B
CN115074771B CN202210824276.6A CN202210824276A CN115074771B CN 115074771 B CN115074771 B CN 115074771B CN 202210824276 A CN202210824276 A CN 202210824276A CN 115074771 B CN115074771 B CN 115074771B
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冯亮亮
尹红艳
黄剑锋
曹丽云
冯永强
付常乐
王宇飞
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Shaanxi University of Science and Technology
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Abstract

The application relates to the technical field of electrocatalysts, and in particular discloses a nitrogen-doped carbon nano tube coated Ni 3 ZnC 0.7 N heterogeneous nanoparticle electrocatalyst and method of making; the preparation method comprises the following steps: taking NiCl 2 ·6H 2 O、Zn(OAc) 2 ·2H 2 Grinding O and dicyandiamide to obtain mixed powder; transferring the mixed powder to a porcelain boat, placing the porcelain boat in a tube furnace under inert atmosphere, performing high-temperature carbonization and reduction, cooling to room temperature, and grinding to obtain a basic electrocatalyst; and (3) treating the basic electrocatalyst with an alkaline solution, alternately cleaning with ethanol and water to be neutral, and drying in vacuum to obtain the electrocatalyst. The application relates to a nitrogen-doped carbon nano tube coated Ni 3 ZnC 0.7 The Ni heterogeneous nanoparticle electrocatalyst has the advantages of low cost, high activity and high stability, the preparation method is simple in process, the synthesis can be successfully performed without preparing a precursor, and the feasibility is high.

Description

Nitrogen-doped carbon nanotube-coated Ni 3 ZnC 0.7 Ni heterogeneous nanoparticle electrocatalyst and preparation method thereof
Technical Field
The application relates to the technical field of electrocatalysts, in particular to a method for coating Ni by nitrogen-doped carbon nano-tubes 3 ZnC 0.7 Ni heterogeneous nanoparticle electrocatalyst and method of making the same.
Background
In order to solve the current growing energy crisis and environmental pollution problems, it is urgent to find a new energy which can be used continuously and is environment-friendly. Hydrogen energy is considered to be one of the most favored new energy sources in the 21 st century because of its environmental protection and high energy utilization. Although the industrial hydrogen production modes are more, in comparison, the hydrogen production by water electrolysis is greatly advantageous in all aspects of raw materials, processes, environmental protection and the like. In addition, the purity of hydrogen produced by the electrolyzed water is higher, so the hydrogen production technology is the best choice for realizing the industrialized development of hydrogen energy at present. Based on the advantages of the electrolysis of water to produce hydrogen, more and more researchers have turned spearhead to the research, but up to now, due to the complex electron transfer process of the electrolysis of water to produce hydrogen mechanism, both from dynamics and thermodynamics, the energy barrier of the reaction process is relatively large, so that a high-performance catalyst is required to improve the efficiency of water splitting.
The catalysts commercially available today are mainly noble metal based electrocatalysts, such as platinum (Pt), iridium (IrO) 2 ) And the like, because the reserves of the catalysts are limited and the cost is high, the long-term industrial application of the catalysts is limited, and therefore, the development of a non-noble metal electrocatalyst with low cost, high activity and high stability is promoted.
Disclosure of Invention
In order to provide a non-noble metal electrocatalyst with low cost, high activity and high stability, the application provides a nitrogen doped carbon nano tube coated Ni 3 ZnC 0.7 Ni heterogeneous nanoparticle electrocatalyst and method of making the same.
In a first aspect, the present application provides a nitrogen-doped carbon nanotube-coated Ni 3 ZnC 0.7 A preparation method of Ni heterogeneous nanoparticle electrocatalyst.
Nitrogen-doped carbon nanotube-coated Ni 3 ZnC 0.7 The preparation method of the Ni heterogeneous nanoparticle electrocatalyst comprises the following steps:
1) The molar ratio is (1-3): 1 respectively taking NiCl 2 ·6H 2 O and Zn (OAc) 2 ·2H 2 O, then according to NiCl 2 ·6H 2 O and Zn (OAc) 2 ·2H 2 Taking the dicyandiamide from the mass sum of O and the dicyandiamide according to the mass ratio of 1:5, and fully grinding the mass sum of O and the dicyandiamide to obtain mixed powder;
2) Transferring the mixed powder to a porcelain boat, placing the porcelain boat in a tube furnace under inert atmosphere, performing carbonization and reduction for 1-4 hours at 500-1000 ℃, cooling to room temperature, and grinding to obtain a basic electrocatalyst;
3) And (3) treating the basic electrocatalyst for 24 hours by using an alkaline solution, alternately cleaning the basic electrocatalyst to be neutral by using ethanol and water, and vacuum drying the basic electrocatalyst for 6 to 8 hours at the temperature of between 60 and 80 ℃ to obtain the electrocatalyst.
Further, the inert atmosphere in the step 2) is Ar gas or H 2 And Ar.
Further, the heating rate of the tube furnace in the step 2) is 5-10 ℃/min.
Further, the air flow rate of the inert atmosphere in the step 2) is 80-100 mL/min.
Further, the alkaline solution in the step 3) is 1M KOH.
Further, the Ni 3 ZnC 0.7 The structure of the Ni heterogeneous nanoparticle electrocatalyst is that the carbon nano tube is embedded with heterogeneous Ni 3 ZnC 0.7 Ni heterogeneous nanoparticles.
In a second aspect, the present application provides a nitrogen-doped carbon nanotube-coated Ni 3 ZnC 0.7 Ni heterogeneous nanoparticle electrocatalyst.
The nitrogen-doped carbon nano tube prepared by the preparation method coats Ni 3 ZnC 0.7 Ni heterogeneous nanoparticle electrocatalyst.
Further, the Ni 3 ZnC 0.7 The structure of the Ni heterogeneous nanoparticle electrocatalyst is that the carbon nano tube is embedded with heterogeneous Ni 3 ZnC 0.7 Ni heterogeneous nanoparticles.
Further, the catalyst was in a 1M KOH solution at 10mA/cm -2 Hydrogen production overpotential at current density of 191mV; at O 2 The initial potential of the oxygen reduction reaction in saturated 0.1M KOH at 1600rpm1.015V, and the half-wave potential is 0.835V.
In summary, the application has the following beneficial effects:
1) According to the application, a simple one-step solid phase method is adopted to synthesize the carbon-coated bimetal carbide structure nano electrocatalytic material with the difunctional characteristic, so that high-efficiency electrocatalytic hydrogen evolution and oxygen reduction reaction are realized, and bimetal active sites of HER and ORR reactions are further creatively realized;
2) The application successfully designs the nitrogen-doped carbon skeleton loaded bimetallic atom group through high-temperature carbonization treatment, and firm metal-C chemical bond is formed between metal atoms and carbon, so that the stability of the catalyst is improved; compared with single metal, the bimetal provides more active sites for hydrogen atoms to adsorb, thereby improving the hydrogen production efficiency; in addition, ni 3 ZnC 0.7 The nano particles show an alloy characteristic, the conductivity of the catalyst is enhanced, and effective electron transmission in the reaction process is ensured; and Ni 3 ZnC 0.7 The heterostructure formed between the catalyst and Ni can provide more catalytic reaction sites and strong depletion and accumulation of electron density, so that the adsorption and desorption energy barrier in the reaction process can be reduced, and the reaction kinetics can be accelerated;
3) The preparation method provided by the application has the advantages of simple process, capability of successfully synthesizing without preparing the precursor, and strong feasibility.
Drawings
FIG. 1 shows a nitrogen-doped carbon-coated Ni prepared in example 1 of the present application 3 ZnC 0.7 XRD pattern of Ni heterogeneous nanoparticle electrocatalyst.
FIG. 2 is a schematic diagram of the present application for regulating NiCl 2 ·6H 2 O and Zn (OAc) 2 ·2H 2 O molar ratio of nitrogen-doped carbon-coated Ni prepared respectively 3 ZnC 0.7 XRD pattern of Ni heterogeneous nanoparticle electrocatalyst.
FIG. 3 shows a nitrogen-doped carbon-coated Ni prepared in example 1 of the present application 3 ZnC 0.7 TEM and HRTEM spectra of Ni heterogeneous nanoparticle electrocatalyst.
FIG. 4 shows a nitrogen-doped carbon-coated Ni prepared in example 1 of the present application 3 ZnC 0.7 Ni heterogeneous nanoparticle electrocatalysisLSV hydrogen production performance curve of the catalyst.
FIG. 5 shows a nitrogen-doped carbon-coated Ni prepared in example 1 of the present application 3 ZnC 0.7 Oxygen reduction performance curve of Ni heterogeneous nanoparticle electrocatalyst.
FIG. 6 shows a nitrogen-doped carbon-coated Ni prepared in two steps according to comparative example 1 of the present application 3 ZnC 0.7 SEM image of Ni heterogeneous nanoparticle electrocatalyst.
FIG. 7 shows a nitrogen-doped carbon-coated Ni prepared in the two-step method of comparative example 1 of the present application 3 ZnC 0.7 XRD pattern of Ni heterogeneous nanoparticle electrocatalyst.
FIG. 8 shows a nitrogen-doped carbon-coated Ni prepared in two steps according to comparative example 1 of the present application 3 ZnC 0.7 Ni heterogeneous nanoparticle electrocatalyst and example 1 LSV hydrogen production performance curve for the one-step preparation catalyst.
Detailed Description
The following examples are given to illustrate the application in further detail, with particular reference to: the following examples, in which no specific conditions are noted, are conducted under conventional conditions or conditions recommended by the manufacturer, and the raw materials used in the following examples are commercially available from ordinary sources except for the specific descriptions.
Examples
Example 1
Nitrogen-doped carbon nanotube-coated Ni 3 ZnC 0.7 The preparation method of the Ni heterogeneous nanoparticle electrocatalyst comprises the following steps:
1) 0.357g of NiCl is taken 2 ·6H 2 O, 0.165g of zinc acetate dihydrate Zn (OAc) 2 ·2H 2 Grinding O and 2.61g of dicyandiamide for 30min to obtain mixed powder;
2) Transferring the mixed powder to a porcelain boat, placing the porcelain boat in a tube furnace under inert atmosphere, heating to 800 ℃ in one step at a heating rate of 10 ℃/min, preserving heat for 2 hours, cooling to room temperature, and grinding to obtain a basic electrocatalyst;
3) The basic electrocatalyst is treated by 0.1M KOH solution for 24 hours, then is alternately washed to be neutral by ethanol and water, and is dried for 8 hours at 60 ℃ in vacuum to obtain the electrocatalyst.
From the figure1, characteristic peaks of the simple Ni substance at 44.4 degrees, 51.7 degrees and 76.3 degrees can be seen; ni was shown at 42.9 °, 50.0 °, 73.3 ° 3 ZnC 0.7 Is a characteristic peak of (2); the characteristic peak of C was shown at 26.5℃and the above results demonstrate successful synthesis of the complex product.
FIG. 2 shows XRD patterns of different catalysts synthesized by controlling the molar ratio of Ni source to Zn source, and it can be seen from FIG. 2 that any ratio adopted in the embodiment can obtain the nitrogen-doped carbon-coated Ni in the present patent 3 ZnC 0.7 Ni heterogeneous nanoparticle electrocatalyst.
It is clear from FIG. 3 that the morphology of the sample is Ni 3 ZnC 0.7 And Ni nanoparticles are heterogeneously embedded in a nitrogen-doped carbon skeleton, which can inhibit agglomeration of the nanoparticles and reaction in an electrolyte.
As can be seen from FIG. 4, 10mA/cm 2 The hydrogen production overpotential of the current density is about 191mV, and the electrochemical hydrogen production activity is excellent.
As can be seen from FIG. 5, at O 2 In saturated 0.1M KOH electrolyte, the oxygen reduction reaction half-wave potential E at 1600rmp 1/2 =0.81V, with good oxygen reduction catalytic activity.
Example 2
Nitrogen-doped carbon nanotube-coated Ni 3 ZnC 0.7 The preparation method of the Ni heterogeneous nanoparticle electrocatalyst comprises the following steps:
1) 0.237g of NiCl was taken 2 ·6H 2 O, 0.109g of Zn (OAc) 2 ·2H 2 Grinding O and 1.73g of dicyandiamide for 30min to obtain mixed powder;
2) Transferring the mixed powder to a porcelain boat, and placing in a tube furnace at H 2 Heating to 800 ℃ at a heating rate of 10 ℃/min in one step under the atmosphere of a mixed gas of Ar, calcining for 2 hours, cooling to room temperature, and grinding to obtain a basic electrocatalyst;
3) The basic electrocatalyst is treated by 0.1M KOH solution for 24 hours, then is alternately washed to be neutral by ethanol and water, and is dried for 8 hours at 60 ℃ in vacuum to obtain the electrocatalyst.
Example 3
Nitrogen-doped carbon nanotube-coated Ni 3 ZnC 0.7 The preparation method of the Ni heterogeneous nanoparticle electrocatalyst is carried out according to the method in the example 2, except that in the step 2), the temperature is raised to 800 ℃ at a heating rate of 10 ℃/min in one step under the argon atmosphere in a tube furnace, and the black product is obtained by calcining for 2 hours, and the obtained black product is alternately washed to be neutral by ethanol and water and then dried, so that the basic electrocatalyst is obtained.
Example 4
Nitrogen-doped carbon nanotube-coated Ni 3 ZnC 0.7 Preparation of Ni heterogeneous nanoparticle electrocatalyst according to example 1, except that NiCl was used in the feedstock 2 ·6H 2 The amount of O added was 0.474g, zn (OAc) 2 ·2H 2 The amount of O added was 0.438g, and the amount of dicyandiamide added was 4.56g.
And 2) heating to 500 ℃ at a heating rate of 5 ℃/min in the tubular furnace under the argon atmosphere in the step 2) for 4 hours to obtain a black product, and alternately cleaning the obtained black product with ethanol and water to neutrality and then drying to obtain the basic electrocatalyst.
Example 5
Nitrogen-doped carbon nanotube-coated Ni 3 ZnC 0.7 Preparation of Ni heterogeneous nanoparticle electrocatalyst according to example 1, except that NiCl was used in the feedstock 2 ·6H 2 The addition amount of O was 0.355g, zn (OAc) 2 ·2H 2 The amount of O added was 0.109g, and the amount of dicyandiamide added was 2.32g.
And 2) heating to 1000 ℃ at a heating rate of 8 ℃/min in the tubular furnace under the argon atmosphere in the step 2) and calcining for 1h to obtain a black product, and alternately cleaning the obtained black product with ethanol and water to neutrality and then drying to obtain the basic electrocatalyst.
Comparative example
Comparative example 1
Nitrogen-doped carbon nanotube-coated Ni 3 ZnC 0.7 The preparation method of the Ni heterogeneous nanoparticle electrocatalyst comprises the following steps:
1) 0.237g of NiCl was taken 2 ·6H 2 O, 0.109g of Zn (OAc) 2 ·2H 2 O and 0.180g of urea are dissolved in a mixed solution of 24ml of ultrapure water and 36ml of methanol, and the mixed solution is magnetically stirred at room temperature to obtain a uniform solution A;
2) Pouring the solution A into a hydrothermal kettle, sealing, and placing the kettle in an oven to perform hydrothermal reaction at 170 ℃ for 17h; cooling to room temperature after the reaction is completed, alternately cleaning the obtained product with ethanol and water, and vacuum drying at 60 ℃ for 8 hours to obtain NiZn-LDH powder;
3) Taking 0.1g of NiZn-LDH powder, taking 0.5g of DCD, and putting the powder into a mortar together for fully grinding for 30min to obtain a powder sample;
4) The powder sample was transferred to a porcelain boat, and then heated to 800 ℃ at a heating rate of 10 ℃/min in a tube furnace under an argon atmosphere and calcined for 2 hours to obtain an electrocatalyst.
As can be seen from fig. 6, the electrocatalyst nanoparticles synthesized by the hydrothermal pretreatment at the same molar ratio are seriously agglomerated, and the nanotube structure is hardly visible, which is unfavorable for the exposure of the catalytically active sites.
As can be seen from FIG. 7, the two-step method can also synthesize complex phase Ni similar to one-step solid phase reaction 3 ZnC 0.7 And a Ni nanocatalyst.
As can be seen from FIG. 8, the HER performance of the two-step synthesis of the nano-electrocatalyst of comparative example 1 is significantly inferior to that of example 1 of the present application, and is embodied in that comparative example 1 drives 10mA/cm 2 While the overpotential required was 329mV, inventive example 1 was only 191mV, demonstrating that the inventive process was simple and better HER activity than the comparative example could be achieved.
Comparative example 2
Nitrogen-doped carbon nanotube-coated Ni 3 ZnC 0.7 The preparation method of the Ni heterogeneous nanoparticle electrocatalyst comprises the following steps:
1) 0.237g of NiCl was taken 2 ·6H 2 O, 0.07g Zn (OAc) 2 ·2H 2 O and 0.180g of urea are dissolved in 50ml of ultrapure water, and the solution A is obtained by magnetic stirring at room temperature;
2) Pouring the solution A into a hydrothermal kettle, sealing, and placing the kettle in an oven to perform hydrothermal reaction at 170 ℃ for 17h; cooling to room temperature after the reaction is completed, alternately cleaning the obtained product with ethanol and water, and vacuum drying at 60 ℃ for 8 hours to obtain NiZn-LDH powder;
3) Taking 0.1g of NiZn-LDH powder, taking 0.5g of DCD, and putting the powder into a mortar together for fully grinding for 30min to obtain a powder sample;
4) The powder sample was transferred to a porcelain boat, and then heated to 800 ℃ at a heating rate of 10 ℃/min in a tube furnace under an argon atmosphere and calcined for 2 hours to obtain an electrocatalyst.
Comparative example 3
1) 0.237g of NiCl was taken 2 ·6H 2 O, 0.219g Zn (OAc) 2 ·2H 2 O and 0.180g of urea are dissolved in 50ml of ultrapure water, and the solution A is obtained by magnetic stirring at room temperature;
2) Pouring the solution A into a hydrothermal kettle, sealing, and placing the kettle in an oven to perform hydrothermal reaction at 170 ℃ for 17h; cooling to room temperature after the reaction is completed, alternately cleaning the obtained product with ethanol and water, and vacuum drying at 60 ℃ for 8 hours to obtain NiZn-LDH powder;
3) Taking 0.1g of NiZn-LDH powder, taking 0.5g of DCD, and putting the powder into a mortar together for fully grinding for 30min to obtain a powder sample;
4) The powder sample was transferred to a porcelain boat, and then heated to 800 ℃ at a heating rate of 10 ℃/min in a tube furnace under an argon atmosphere and calcined for 2 hours to obtain an electrocatalyst.

Claims (8)

1. Nitrogen-doped carbon nanotube-coated Ni 3 ZnC 0.7 The preparation method of the Ni heterogeneous nanoparticle electrocatalyst is characterized by comprising the following steps of:
1) The molar ratio is (1-3): 1 respectively taking NiCl 2 •6H 2 O and Zn (OAc) 2 •2H 2 O, then according to NiCl 2 •6H 2 O and Zn (OAc) 2 •2H 2 Taking the dicyandiamide from the mass sum of O and the dicyandiamide according to the mass ratio of 1:5, and fully grinding the mass sum of O and the dicyandiamide to obtain mixed powder;
2) Transferring the mixed powder to a porcelain boat, placing the porcelain boat in a tube furnace, performing carbonization and reduction for 1-4 hours at 500-1000 ℃, cooling to room temperature, and grinding to obtain a basic electrocatalyst;
3) Treating the basic electrocatalyst with an alkaline solution for 24 hours, alternately cleaning with ethanol and water to be neutral, and vacuum drying at 60-80 ℃ for 6-8 hours to obtain the nitrogen-doped carbon nanotube-coated Ni 3 ZnC 0.7 Ni heterogeneous nanoparticle electrocatalyst;
the nitrogen-doped carbon nano tube is coated with Ni 3 ZnC 0.7 The structure of the Ni heterogeneous nanoparticle electrocatalyst is carbon nano tube embedded heterogeneous Ni 3 ZnC 0.7 Ni heterogeneous nanoparticles.
2. A nitrogen-doped carbon nanotube-coated Ni as recited in claim 1 3 ZnC 0.7 The preparation method of the Ni heterogeneous nanoparticle electrocatalyst is characterized by comprising the following steps of: the inert atmosphere in the step 2) is Ar gas or H 2 And Ar.
3. A nitrogen-doped carbon nanotube-coated Ni as recited in claim 1 3 ZnC 0.7 The preparation method of the Ni heterogeneous nanoparticle electrocatalyst is characterized by comprising the following steps of: and in the step 2), the heating rate of the tube furnace is 5-10 ℃/min.
4. A nitrogen-doped carbon nanotube-coated Ni as recited in claim 1 3 ZnC 0.7 The preparation method of the Ni heterogeneous nanoparticle electrocatalyst is characterized by comprising the following steps of: the air flow rate of the inert atmosphere in the step 2) is 80-100 mL/min.
5. A nitrogen-doped carbon nanotube-coated Ni as recited in claim 1 3 ZnC 0.7 The preparation method of the Ni heterogeneous nanoparticle electrocatalyst is characterized by comprising the following steps of: the alkaline solution in the step 3) is 1M KOH.
6. A nitrogen-doped carbon nanotube-coated Ni prepared by the method of any one of claims 1 to 5 3 ZnC 0.7 Ni heterogeneous nanoparticle electrocatalyst.
7. The nitrogen-doped carbon nanotube-coated Ni of claim 6 3 ZnC 0.7 The Ni heterogeneous nanoparticle electrocatalyst is characterized in that: the nitrogen-doped carbon nano tube is coated with Ni 3 ZnC 0.7 The structure of the Ni heterogeneous nanoparticle electrocatalyst is that the carbon nano tube is embedded with heterogeneous Ni 3 ZnC 0.7 Ni heterogeneous nanoparticles.
8. The nitrogen-doped carbon nanotube-coated Ni of claim 6 3 ZnC 0.7 The Ni heterogeneous nanoparticle electrocatalyst is characterized in that: the catalyst was in 1M KOH solution, 10mA/cm -2 Hydrogen production overpotential at current density of 191mV; at O 2 In saturated 0.1M KOH, the oxygen reduction reaction has an initial potential of 1.015V and a half-wave potential of 0.835V at 1600 rpm.
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