CN108823597A - Annealing method prepares the method and its application of the nickel sulfide liberation of hydrogen catalyst of N doping - Google Patents
Annealing method prepares the method and its application of the nickel sulfide liberation of hydrogen catalyst of N doping Download PDFInfo
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- CN108823597A CN108823597A CN201810454397.XA CN201810454397A CN108823597A CN 108823597 A CN108823597 A CN 108823597A CN 201810454397 A CN201810454397 A CN 201810454397A CN 108823597 A CN108823597 A CN 108823597A
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Abstract
The invention belongs to electrocatalytic hydrogen evolution technical fields; it is related to a kind of method that annealing method prepares the nickel sulfide liberation of hydrogen catalyst of N doping; thiocarbamide is weighed in porcelain boat; move to the upstream of temperature programming tube furnace; the a piece of nickel foam pre-processed is taken to be placed in another porcelain boat; move to downstream, be warming up to 300~500 DEG C of 30~100min of sintering soak under inert gas protection, after naturally cool to after room temperature to obtain the final product.The present invention is also by obtained catalyst, as working electrode, the electrolysis water liberation of hydrogen under alkaline condition.For the present invention using nickel foam as substrate, thiocarbamide changed dramatically Ni by the nickel sulfide elctro-catalyst for the N doping that a step annealing method synthesizes as sulphur source and nitrogen source3S2Form and electronic structure, expose more surface-active sites, increase conductivity, enhance evolving hydrogen reaction activity.The disadvantages of various sulfide conductivity that the present invention solves nickel are low, and surface-active site is few, improves its electrocatalytic hydrogen evolution performance, and the excellent stability in alkalinity, is expected to industrialize.
Description
Technical field
The invention belongs to electrocatalytic hydrogen evolution technical fields, are related to the preparation of liberation of hydrogen catalyst, in particular to a kind of annealing method
Prepare the method and its application of the nickel sulfide liberation of hydrogen catalyst of N doping.
Background technique
The development of today's society is overly dependent upon fossil fuel, and fossil fuel consume excessively exacerbate environmental pollution and
Energy crisis.Therefore, exploitation cleaning, renewable and environmental-friendly fungible energy source are extremely urgent.It compares various alternative
The energy, hydrogen is since its fuel value is high and combustion product only has water, it is considered to be replace conventional fossil fuel most has prospect
Energy carrier.Electrolysis water hydrogen making is considered as a kind of green and sustainable hydrogen production process.Noble metal such as platinum base
Catalyst has excellent evolving hydrogen reaction（HER）Activity, but its application is greatly limited since reserves at high cost are low, so anxious
It need to seek evolving hydrogen reaction catalyst more cheap and easy to get.
Various nickel-base catalysts are widely used in electrocatalytic hydrogen evolution field in recent years, and typical example has the various sulphur of nickel
Compound, selenides, oxide, hydroxide and various nickel alloys.The various sulfide of nickel are due to its good conductivity and in alkali
Property medium in stability it is high, to be considered as a kind of promising evolving hydrogen reaction（HER）Catalyst.But it reports at present
The various sulfide about nickel catalytic activity it is still lower.Studies have shown that the activity and the coordination of surface S atom of nickel sulfide
Several and neighbouring Ni atomic charge exhausts highly relevant.Therefore, nitrogen can be passed through（N）Doping is to improve hydrogen adsorption free energy in turn
Improve the evolving hydrogen reaction activity of nickel sulfide.
There is presently no the nickel sulfides about N doping（N-Ni3S2/NF）Electrocatalytic hydrogen evolution of the nano material in alkalinity
The research report of energy.
Summary of the invention
The nickel sulfide of N doping is prepared it is an object of the invention to disclose a kind of annealing method（N-Ni3S2/NF）Liberation of hydrogen catalysis
The method of agent.
Technical solution：
The method that annealing method prepares the nickel sulfide liberation of hydrogen catalyst of N doping, specific step is as follows：
The ratio that a piece of nickel foam pre-processed is corresponded to according to 0.5~2 g thiocarbamide, weighs thiocarbamide in porcelain boat, is transferred to journey
The upstream of sequence heating tube furnace, then takes the nickel foam pre-processed to be placed in another porcelain boat, moves under temperature programming tube furnace
Trip, is warming up to 300~500 DEG C of 30~100min of sintering soak under inert gas protection and takes after room temperature
Out to obtain the final product.
In more excellent disclosed example of the invention, the nickel foam pre-processed, is that nickel foam is cut into a certain size, according to
It is secondary to be cleaned by ultrasonic 15~30min with hydrochloric acid and acetone, the oxide on its surface is removed, then each super with dehydrated alcohol and deionized water
Sound 2~3 times, 5~10min, is finally dried in vacuo every time, obtains pretreatment nickel foam.
In more excellent disclosed example of the invention, the inert gas is nitrogen.
In more excellent disclosed example of the invention, the heating rate is 5 DEG C/min.
In more excellent disclosed example of the invention, the ratio that preferably 1 g thiocarbamide corresponds to a piece of nickel foam pre-processed, in inertia
The lower 400 DEG C of sintering soak 90min of gas shield.
For convenient for comparison, the invention discloses a kind of preparation method of hydro-thermal method synthesis nickel sulfide Electrocatalytic Activity for Hydrogen Evolution Reaction agent, packets
It includes：Solution is prepared according to the ratio that 2~2.5 g thiocarbamides are added in 15~25 mL deionized waters, is transferred to 50 mL after ultrasonic disperse
Polytetrafluoroethyllining lining reaction kettle, then take a piece of preprocessed good nickel foam inclination to be put into reaction kettle and be immersed in molten
It in liquid, by reaction kettle in 100~150 DEG C of 4~6h of heat preservation, is cooled to room temperature, sample is taken out, with deionized water and dehydrated alcohol
Washing repeatedly, is finally dried in vacuo, nickel sulfide can be obtained respectively（Ni3S2/NF）, disperse 2.2 in preferably 20 mL deionized waters
G thiocarbamide, 150 DEG C of heat preservation 5h.
A further object of the invention is for obtained catalyst as working electrode, to be applied under alkaline condition
Electrolysis water liberation of hydrogen.
The present invention utilizes x-ray diffractometer（XRD）, x-ray photoelectron spectroscopy（XPS）, scanning electron microscope (SEM) photograph（SEM）, with
Potassium hydroxide（KOH）Solution is that target carries out electrocatalytic decomposition water collecting gas, by analyzing electrochemical tests（LSV）With
Tafel curve（Tafel plot）, to assess its electrocatalytic decomposition elutriation hydrogen activity.
32The electro catalytic activity of elctro-catalyst is tested：
（1）Compound concentration is the KOH solution of 1 mol/L, and the solution prepared is sealed and is placed in dark place；
（2）Take CHI760 electrochemical workstation（Shanghai Chen Hua Instrument Ltd.）Electricity is carried out to sample in three-electrode system
Chemical property test.It is to electrode with carbon-point, saturated calomel electrode (SCE) is reference electrode, N-Ni3S2Material is working electrode.
Linear sweep voltammetry is used in the KOH electrolyte of 1 mol/L（LSV）Test can be carried out to the electrochemistry of electrode material.
The advantage of the invention is that：
（1）Using porous foam nickel as conductive substrates and nickel source, thiocarbamide is directly being steeped as sulphur source and nitrogen source by a step annealing method
Foam nickel surface grows nickel sulfide nano-wire, while introducing nitrogen into nickel sulfide, and method is simple；
（2）Nickel sulfide is directly grown in nickel foam, and N doping is carried out to nickel sulfide, can accelerate the transmission of electronics.Meanwhile sulphur
Catalyst stability in alkaline medium can be improved in this strong interaction changed between nickel and nickel foam；
（3）Gained Ni of the invention3S2Material is used for electrocatalytic hydrogen evolution catalyst, the N-Ni of optimization3S2NWs material is in alkaline condition
Under, it is 10 mA/cm in current density2When, overpotential reaches 105 mV, and its Tafel slope is only 108mV dec-1。
Beneficial effect
Because of porous foam nickel（NF）With unique three-dimensional structure, so not only increasing surface as conductive substrates and nickel source
Product, and product is also simple and easy to get.For the present invention using nickel foam as substrate, thiocarbamide passes through a step annealing method as sulphur source and nitrogen source
The nickel sulfide of the N doping of synthesis（N-Ni3S2/NF）Elctro-catalyst changed dramatically Ni3S2Form and electronic structure, exposure
More surface-active sites, increase conductivity, and then enhance evolving hydrogen reaction activity.N doping synthesized by the present invention
Nickel sulfide（N-Ni3S2/NF）Elctro-catalyst, the various sulfide conductivity for solving nickel are low, and surface-active site is equal less to be lacked
Point improves its electrocatalytic hydrogen evolution performance, and the excellent stability in alkalinity.
Detailed description of the invention
Fig. 1（a）For Ni3S2The SEM figure of/NF NRs under high-resolution and low resolution；
（b）For N-Ni3S2The SEM figure of/NF NWs under high-resolution and low resolution.
Fig. 2（a）For N-Ni3S2The longitudinal profile SEM figure of/NF NWs under low resolution；
（b）For N-Ni3S2The longitudinal profile SEM figure of/NF NWs at high resolutions.
Fig. 3（a）For blank nickel foam（NF）XRD diagram；
（b, c, d）Respectively NF, Ni3S2/ NF NRs and N-Ni3S2The EDS of/NF NWs schemes.
Fig. 4（a）For Ni3S2/ NF NRs and N-Ni3S2The XRD diagram of/NF NWs；
（b, c, d）Respectively N-Ni3S2The XPS figure of Ni 2p, S 2p, N 1s in/NF NWs.
Fig. 5, N-Ni3S2The hydrogen evolution activity test of/NF NWs electrocatalysis material in alkaline medium (1.0M KOH)：
Wherein（a）For NF, Ni3S2/ NF NRs and N-Ni3S2Polarization curve of/NF the NWs and Pt/NF in 1.0M KOH；
（b）For NF, Ni3S2/ NF NRs and N-Ni3S2The Tafel slope of/NF NWs and Pt/NF in 1.0M KOH；
（c）For NF, Ni3S2/ NF NRs and N-Ni3S2The electrochemical impedance figure of/NF NWs in 1.0M KOH；
（d）For Ni3S2/ NF NRs and N-Ni3S2Polarization curve of/NF the NWs in alkaline (1.0M KOH) after 2000 circle of circulation,
Illustration is the stability test under certain current density.
Specific embodiment
Below with reference to specific implementation example, the present invention will be further described, so that those skilled in the art more fully understand
The present invention, but the invention is not limited to following embodiments.
Comparative test
Hydro-thermal method synthesizes the agent of nickel sulfide Electrocatalytic Activity for Hydrogen Evolution Reaction, weighs 2~2.5 g thiocarbamides in beaker, and 15~25 mL deionizations are added
Water is transferred to the polytetrafluoroethyllining lining reaction kettle of 50 mL after ultrasonic disperse, a piece of preprocessed good nickel foam is then taken to incline
It is tiltedly put into reaction kettle and submerges in the solution, reaction kettle is placed in 4~6h of heat preservation in 100~150 DEG C of baking ovens, is cooled to room
Temperature takes out sample, is washed repeatedly respectively with deionized water and dehydrated alcohol, be finally dried in vacuo, nickel sulfide can be obtained
（Ni3S2/NF）, preferably 2.2 g thiocarbamides are scattered in 20 mL deionized waters, keep the temperature 5h in 150 DEG C of baking ovens.
Embodiment 1
The method that annealing method prepares the nickel sulfide liberation of hydrogen catalyst of N doping weighs 0.5 g thiocarbamide and is placed in porcelain boat, and by its turn
The upstream of temperature programming tube furnace is moved to, then takes a piece of nickel foam handled well to be placed in another porcelain boat, and transfer them to journey
Temperature programming tube furnace is heated to 400 under nitrogen protection with the heating rate of 5 DEG C/min by the downstream of sequence heating tube furnace
90min is kept the temperature after DEG C, after room temperature, is taken out to get the nickel sulfide of N doping is arrived（N-Ni3S2/NF）.
Embodiment 2
The method that annealing method prepares the nickel sulfide liberation of hydrogen catalyst of N doping weighs 1.0 g thiocarbamides and is placed in porcelain boat, and by its turn
The upstream of temperature programming tube furnace is moved to, then takes a piece of nickel foam handled well to be placed in another porcelain boat, and transfer them to journey
Temperature programming tube furnace is heated to 400 under nitrogen protection with the heating rate of 5 DEG C/min by the downstream of sequence heating tube furnace
90min is kept the temperature after DEG C, after room temperature, is taken out to get the nickel sulfide of N doping is arrived（N-Ni3S2/NF）.
Embodiment 3
The method that annealing method prepares the nickel sulfide liberation of hydrogen catalyst of N doping weighs 1.5 g thiocarbamides and is placed in porcelain boat, and by its turn
The upstream of temperature programming tube furnace is moved to, then takes a piece of nickel foam handled well to be placed in another porcelain boat, and transfer them to journey
Temperature programming tube furnace is heated to 400 under nitrogen protection with the heating rate of 5 DEG C/min by the downstream of sequence heating tube furnace
90min is kept the temperature after DEG C, after room temperature, is taken out to get the nickel sulfide of N doping is arrived（N-Ni3S2/NF）.
Embodiment 4
The method that annealing method prepares the nickel sulfide liberation of hydrogen catalyst of N doping weighs 2.0 g thiocarbamides and is placed in porcelain boat, and by its turn
The upstream of temperature programming tube furnace is moved to, then takes a piece of nickel foam handled well to be placed in another porcelain boat, and transfer them to journey
Temperature programming tube furnace is heated to 400 under nitrogen protection with the heating rate of 5 DEG C/min by the downstream of sequence heating tube furnace
90min is kept the temperature after DEG C, after room temperature, is taken out to get the nickel sulfide of N doping is arrived（N-Ni3S2/NF）.
Embodiment 5
The method that annealing method prepares the nickel sulfide liberation of hydrogen catalyst of N doping weighs 1.0 g thiocarbamides and is placed in porcelain boat, and by its turn
The upstream of temperature programming tube furnace is moved to, then takes a piece of nickel foam handled well to be placed in another porcelain boat, and transfer them to journey
Temperature programming tube furnace is heated to 300 under nitrogen protection with the heating rate of 5 DEG C/min by the downstream of sequence heating tube furnace
90min is kept the temperature after DEG C, after room temperature, is taken out to get the nickel sulfide of N doping is arrived（N-Ni3S2/NF）.
Embodiment 6
The method that annealing method prepares the nickel sulfide liberation of hydrogen catalyst of N doping weighs 1.0 g thiocarbamides and is placed in porcelain boat, and by its turn
The upstream of temperature programming tube furnace is moved to, then takes a piece of nickel foam handled well to be placed in another porcelain boat, and transfer them to journey
Temperature programming tube furnace is heated to 500 under nitrogen protection with the heating rate of 5 DEG C/min by the downstream of sequence heating tube furnace
90min is kept the temperature after DEG C, after room temperature, is taken out to get the nickel sulfide of N doping is arrived（N-Ni3S2/NF）.
The characterization and electro catalytic activity experimental analysis of obtained elctro-catalyst：
As shown in Figure 1, it can be seen that Ni from figure a3S2The presentation of/NF pattern is rodlike, and length is about 1 μm, and diameter is about 300nm,
It can be seen that N-Ni from figure b3S2/ NF pattern is linear；
N-Ni as can be seen from Figure 23S2/ NFNWs length is about 5.89 μm, and diameter is 30~80nm；
As shown in figure 3, it can be seen that the rodlike Ni synthesized through hydro-thermal reaction from figure c3S2/ NF not Nitrogen element, and from d figure
It can be seen that the linear Ni of annealed reaction synthesis3S2Nitrogen is introduced in/NF；
As shown in figure 4, from figure（a）In it can be seen that at 21.8 °, 31.1 °, 37.8 °, 44.3 °, 50.1 °, and 55.3 °
Diffraction maximum and Ni3S2The map of (JCPDF# 44-1418) is consistent, and at 44.8 °, 52.2 ° and 76.8 ° and blank foam
The map of nickel (JCPDF# 03-1051) is consistent；From figure（b）As can be seen that the peak of 856.1 eV and 874.2 eV are Ni 2p3/2
With Ni p1/2Spin(-)orbit it is bimodal, the spike of 852.9 eV may be the peak of foam nickel base；From figure（c）As can be seen that
The bimodal of 162.7 eV and 163.5 eV may be S 2p3/2With S 2p1/2Peak；Peak at 161.7 eV may be Ni3S2In
The peak of S-Ni；Scheming（d）In 398 eV at peak and figure（b）In 870.2 eV at peak may be Ni-N peak, these
All show that nitrogen has successfully been introduced into Ni3S2In；
As shown in figure 5, figure（a）In be apparent that N-Ni3S2/ NFNWs electrocatalysis material has excellent electricity in alkalinity
Catalytic hydrogen evolution performance is 10mA/cm in current density2And 100mA/cm2Overpotential compared with NF and Ni3S2/ NF NRs obviously drops
It is low；Figure（b）It has been shown that, N-Ni3S2The Tafel slope of/NFNWs electrocatalysis material is compared with NF and Ni3S2/ NF NRs is smaller, illustrates that it is anti-
Answer kinetics increase；（c）It can be seen that N-Ni in figure3S2/ NFNWs electrocatalysis material electrochemical impedance is compared with NF and Ni3S2/NF
NRs is small, illustrates that electron transfer rate is fast；（d）It can see in figure, in alkaline medium, after 2000 circle of CV circulation, N-
Ni3S2/ NF NWs electrocatalysis material shows preferable stability, and Ni3S2The stability of/NF NRs is relatively poor；From i-t
Curve is it can also be seen that N-Ni3S2The current density of/NFNWs electrocatalysis material does not decay significantly.
The above description is only an embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair
Equivalent structure or equivalent flow shift made by bright specification is applied directly or indirectly in other relevant technical fields,
Similarly it is included within the scope of the present invention.
Claims (7)
1. the method that annealing method prepares the nickel sulfide liberation of hydrogen catalyst of N doping, which is characterized in that specific step is as follows：According to
0.5~2 g thiocarbamide corresponds to the ratio of a piece of nickel foam pre-processed, weighs thiocarbamide in porcelain boat, is transferred to temperature programming pipe
Then the upstream of formula furnace takes a piece of nickel foam pre-processed to be placed in another porcelain boat, moves to the downstream of temperature programming tube furnace,
300~500 DEG C of 30~100min of sintering soak are warming up under inert gas shielding to take out after room temperature to obtain the final product.
2. the method that annealing method prepares the nickel sulfide liberation of hydrogen catalyst of N doping according to claim 1, it is characterised in that：Institute
The nickel foam pre-processed is stated, is that nickel foam is cut into 2 × 3 cm sizes, successively with hydrochloric acid and the acetone ultrasound of 3 mol/L
15~30min is cleaned, removes the oxide on its surface, then each ultrasonic 2~3 times with dehydrated alcohol and deionized water, every time 5~
10min, 60 DEG C of vacuum drying obtain pretreatment nickel foam.
3. the method that annealing method prepares the nickel sulfide liberation of hydrogen catalyst of N doping according to claim 1, it is characterised in that：Institute
Stating inert gas is nitrogen.
4. the method that annealing method prepares the nickel sulfide liberation of hydrogen catalyst of N doping according to claim 1, it is characterised in that：Institute
Stating heating rate is 5 DEG C/min.
5. the method that annealing method prepares the nickel sulfide liberation of hydrogen catalyst of N doping according to claim 1, it is characterised in that：It presses
The ratio of a piece of nickel foam pre-processed is corresponded to according to 1 g thiocarbamide, under inert gas protection 400 DEG C of sintering soak 90min.
6. the nickel sulfide liberation of hydrogen catalyst of N doping made from -5 any the methods according to claim 1.
7. a kind of application of the nickel sulfide liberation of hydrogen catalyst of N doping described in claim 6, it is characterised in that：As work
Electrode, the electrolysis water liberation of hydrogen under alkaline condition.
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| CN110201697A (en) * | 2019-05-29 | 2019-09-06 | 浙江大学 | A kind of three-dimensional N doping transition metal oxide/vulcanization nickel composite catalyst and preparation method and application |
| CN110180574A (en) * | 2019-06-05 | 2019-08-30 | 北京工业大学 | A kind of preparation of N doping ternary sulfide electrocatalyst materials and application |
| CN111617780A (en) * | 2020-03-10 | 2020-09-04 | 华中师范大学 | Nitrogen-doped nickel-molybdenum-based composite sulfide for stably producing hydrogen by electrolyzing water and preparation method |
| CN111977708A (en) * | 2020-06-23 | 2020-11-24 | 江苏大学 | Preparation method of nitrogen-doped transition metal sulfide and application of nitrogen-doped transition metal sulfide to electrolyzed water |
| CN113416976A (en) * | 2021-05-31 | 2021-09-21 | 江苏大学 | Cu5FeS4/Ni3S2Preparation method of @ NF composite material and application of @ NF composite material in photoelectric hydrolysis |
| CN113668007A (en) * | 2021-07-23 | 2021-11-19 | 兰州大学 | Hydrogen evolution catalyst and preparation method and application thereof |
| CN113668007B (en) * | 2021-07-23 | 2023-05-05 | 兰州大学 | Hydrogen evolution catalyst and preparation method and application thereof |
| CN115341166A (en) * | 2022-10-19 | 2022-11-15 | 有研工程技术研究院有限公司 | Preparation method of nickel-based vulcanized material |
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