CN109898097A - Monatomic iron-the carbon-coating of immersion-type modifies Ni-based or cobalt-based composite electrode preparation method and applications - Google Patents
Monatomic iron-the carbon-coating of immersion-type modifies Ni-based or cobalt-based composite electrode preparation method and applications Download PDFInfo
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Abstract
The invention belongs to electrochemical technology fields, it is related to the monatomic iron-carbon-coating of immersion-type and modifies Ni-based or cobalt-based composite electrode preparation method: prepares the ethanol solution of tannic acid and ferric nitrate respectively, iron nitrate solution is slowly added dropwise to tan-liquor collagen solution under room temperature；Then will grow in carbon paper, carbon cloth, electro-conductive glass or stainless (steel) wire have Ni-based or cobalt-based base material to be impregnated in colloidal solution, after taking-up with sulphur source or phosphorus source or nitrogen source or other raw materials are not added, calcine 0.5~4 h under inert gas protection, it is cooling after to obtain the final product.Raw material of the present invention is cheap and easy to get, nontoxic, operation is simple, can coated a variety of substrates, the reaction time is short, is easy to industrialize.Obtained composite electrode has preferable pattern retentivity and good chemical property and stability, can be used as electrode for electrocatalytic decomposition water oxygen evolution reaction.It is 40 mA cm in current density when composite material obtained by the present invention is used as electrocatalytic decomposition water anode‑2When overpotential up to 280 mV.
Description
Technical field
The invention belongs to electrochemical technology fields, are related to the monatomic iron of immersion-type-carbon-coating decorative material preparation method, especially
It is related to a kind of monatomic iron-carbon-coating of immersion-type and modifies Ni-based or cobalt-based composite electrode preparation method and applications.
Background technique
Oxygen evolution reaction (OER) is the important link of water decomposition and solar fuel cell, however, complicated polyelectron transmission
Hinder its dynamic process.Effective elctro-catalyst is to speed up reaction rate and reduces reaction overpotential, to improve energy
Measure the key of transfer efficiency.Therefore, it finds and optimizes efficient elctro-catalyst and attracted extensive attention.
So far, the elements such as Fe, Co, Ni based on rich content in the earth's crust have been reported and prepare alloy and compound, show
Out close to the catalytic performance of noble metal Ir/Ru.Wherein, micro Fe element is introduced in Ni/Co sill, can greatly be promoted
The OER activity of Ni/Co sill.However under conditions of the preparation of these composite materials is limited to doping or mixes,
When practical application, this synthesis mode often may require that great cost input, and overpotential and stability still need to further mention
It rises.Therefore, preparing high-efficient, good stability Fe, Co, Ni base analysis oxygen elctro-catalyst is still a times with challenge
Business.
In recent years, monatomic catalyst gets more and more people's extensive concerning because its atom maximally utilizes rate.But partial size is got over
Small its surface free energy that will lead to increases, more easy to reunite.In order to reduce this influence, researchers will be each by organic ligand
Metal ion is fixed in its structure, and more stable monatomic material has successfully been obtained.However at present for monoatomic research
Still it is confined in single metal complex, significantly limits the development of monatomic material.Therefore, a kind of immersion-type is designed
Monatomic decorative material is significantly to work.
So far, not yet discovery is using the monatomic iron of immersion-type-Ni-based or cobalt-based composite electrode of carbon-coating modification.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the invention to disclose the monatomic iron-of immersion-type
Carbon-coating modifies Ni-based or cobalt-based composite electrode preparation method.
A kind of monatomic iron-carbon-coating of immersion-type modifies Ni-based or cobalt-based composite electrode preparation method, including as follows
Step:
A, tannic acid is added in ethyl alcohol the ratio for being the mL of 0.1~20 g:5~20 according to solid-to-liquid ratio, and stirring forms solution A, excellent
Selecting solid-to-liquid ratio is 1 g:10 mL；
B, Fe(NO3)39H2O is dissolved in ethyl alcohol and forms solution B by the ratio for being the mL of 0.1~20 g:5~20 according to solid-to-liquid ratio, excellent
Selecting solid-to-liquid ratio is 0.2 g:10 mL；
C, solution B is slowly added dropwise into solution A, stirring forms colloidal solution；
D, about 1 × 2 cm of size is taken2Ni-based or cobalt-based base material has been grown, 1~24 h in above-mentioned colloidal solution is immersed in,
It is preferred that 6 h, take out, drying obtains presoma Fe-G/Ni-Sub or Fe-G/Co-Sub；
E, the presoma Fe-G/Ni-Sub or Fe-G/Co-Sub of drying are transferred in semi-enclosed porcelain boat, sulphur source or phosphorus source is added
Or nitrogen source, or other raw materials are not added, it is then transferred to high-temperature calcination under inert gas protection in temperature programming tube furnace
0.5~4h, preferably 1 h, after room temperature, take out to get.
In the more excellent disclosed example of the present invention, it is in carbon paper (CP), carbon that Ni-based or cobalt-based base material has been grown described in step D
Growth has the compound or simple substance of nickel or cobalt on cloth (CC), electro-conductive glass (FTO) or stainless (steel) wire (SSM)；Wherein, the nickel
Compound or simple substance are nickel hydroxide, nickel oxide or amorphous nickel；The compound or simple substance of the cobalt are cobalt hydroxide, cobalt oxide
Or amorphous cobalt.
In the more excellent disclosed example of the present invention, sulphur source described in step E is sulphur powder, sublimed sulfur or thiocarbamide；Phosphorus source is time phosphorous
Sour sodium, red phosphorus or white phosphorus；The nitrogen source is ammonia, urea or melamine；The calcination temperature is 300~500 DEG C, heating rate
For 10 DEG C/min, the inert gas is nitrogen or argon gas.
Tannic acid, Chinese nickname are tannic acid, tannic acid, gallic acid, tannin, larch extract, two gallic acids, charcoal Buddhist nun again
Acid, soft acid etc..
A further object of the invention is, obtained monatomic iron-carbon-coating is modified Ni-based or cobalt-based composite material,
Applied to electrocatalytic decomposition water positive electrode.
Transmission electron microscope is corrected using x-ray diffractometer (XRD), scanning electron microscope (SEM) and spherical aberration
(aberration-corrected HAADF-STEM) carries out micromorphology analysis to product, is with potassium hydroxide (KOH) solution
Target carries out the experiment of electrocatalytic decomposition elutriation oxygen, by analyzing electrochemical tests (LSV), to assess its electrocatalytic decomposition water
Oxygen evolution activity.
Monatomic iron-carbon-coating modifies Ni-based or cobalt-based composite material electro catalytic activity experiment:
(1) compound concentration is 1 mol L-1The solution prepared is sealed and is placed in dark place by KOH solution；
(2) CHI660 electrochemical workstation (Shanghai Chen Hua Instrument Ltd.) is taken to carry out electricity to sample in three-electrode system
Chemical property test.It is to electrode with platinum guaze, mercuric oxide electrode (Hg/HgO) is reference electrode, and obtained composite material is work
Make electrode, in 1 mol L-1In KOH electrolyte using linear sweep voltammetry (LSV) to the chemical property of electrode material into
Row test.
The made monatomic iron of the present invention-carbon-coating modifies Ni-based or cobalt-based composite material, compared to simple Ni-based or cobalt-based
Material shows lower electrocatalytic decomposition water oxygen evolution reaction overpotential.Wherein, monatomic iron-carbon-coating obtained by the present invention
It is 40 mA cm in current density when modifying nanometer nickel sulfide piece composite material as electrocatalytic decomposition water positive electrode-2When mistake
Current potential is up to 280 mV.
Beneficial effect
Operation of the present invention is simple for process, can it is coated in a variety of differences are Ni-based or the substrate of cobalt-based material on, be easy to industrialize
Implement.Obtained composite electrode has preferable pattern retentivity, and preferable chemical property and stability, raw material
Cheap and easy to get, nontoxic, simple process can be used for electrocatalytic decomposition water oxygen evolution reaction directly as electrode.
Detailed description of the invention
Fig. 1 is prepared simple vulcanization nickel nano film (NiS2NS) and monatomic iron-carbon-coating modifies nanometer nickel sulfide piece
(Fe-C/NiS2NS) X-ray diffraction (XRD) spectrogram of composite sample, wherein abscissa is the angle of diffraction (2 θ), and unit is
It spends (o), ordinate is diffracted intensity (Intensity), unit cps.
Fig. 2 is prepared simple vulcanization nickel nano film (NiS2NS) and monatomic iron-carbon-coating modifies nanometer nickel sulfide piece
(Fe-C/NiS2NS) scanning electron microscope (SEM) photo of composite sample.
Monatomic iron prepared by Fig. 3-carbon-coating modifies nanometer nickel sulfide piece (Fe-C/NiS2NS) composite sample is high
Angle annular dark field scanning transmission microscope (HAADF-STEM) photo.
Fig. 4 is simple vulcanization nickel nano film (NiS2NS) and monatomic iron-carbon-coating modifies nanometer nickel sulfide piece (Fe-C/
NiS2NS) composite material and the monatomic iron-carbon-coating are pervasive to vulcanization cobalt nanowire (CoS2NW), nickel oxide nano piece
(NiO NS) and nickel sulfide nanoparticles (NiS2NP) sample electrocatalytic decomposition elutriation oxygen in different Ni-based or cobalt-based substrates
Polarization curve and Tafel curve figure.
Specific embodiment
The following describes the present invention in detail with reference to examples, so that those skilled in the art more fully understand this hair
It is bright, but the invention is not limited to following embodiments.
Unless otherwise defined, term (including scientific and technical terminology) used herein above should be construed as having as belonging to the present invention
The identical meaning that those skilled in the art are commonly understood by.It will also be understood that term used herein above should be explained
To have the meaning consistent with their meanings in the content of this specification and the relevant technologies, and should not be with idealization
Or excessive form is explained, unless expressly so limiting here.
Embodiment 1
The preparation of iron-carbon (Fe-C) electrode is using dipping-calcining method: 0.1 g tannic acid is weighed in 50 mL beakers,
5 mL ethanol solutions are added thereto, magnetic agitation to Quan Rong forms solution A；It weighs 0.1 g Fe(NO3)39H2O and is dissolved in 5 mL
Solution B is formed in ethanol solution；Gained clear solution B is slowly added drop-wise in solution A, 2 h of room temperature magnetic agitation, forms colloid
Solution C.Take about 1 × 2 cm of size2Carbon cloth (CC or carbon paper CP or electro-conductive glass FTO or stainless (steel) wire SSM) be immersed in colloid
About 1 h in solution C takes out, is put into baking oven, 60 DEG C of 6 h of drying.By above-mentioned impregnated carbon cloth, (CC or carbon paper CP are led again
Electric glass FTO or stainless (steel) wire SSM) it is transferred in semiclosed porcelain boat, it is then transferred in temperature programming tube furnace, in Ar gas shielded
Under, temperature programming tube furnace is heated to keep the temperature 1 h after 350 DEG C with the heating rate of 10 DEG C/min, after naturally cool to room temperature
Afterwards, it takes out.
Embodiment 2
The preparation of iron-carbon (Fe-C) electrode is using dipping-calcining method: 0.1 g tannic acid is weighed in 50 mL beakers,
5 mL ethanol solutions are added thereto, magnetic agitation to Quan Rong forms solution A；It weighs 0.1 g Fe(NO3)39H2O and is dissolved in 5 mL
Solution B is formed in ethanol solution；Gained clear solution B is slowly added drop-wise in solution A, 2 h of room temperature magnetic agitation, forms colloid
Solution C.Take about 1 × 2 cm of size2Carbon cloth (CC or carbon paper CP or electro-conductive glass FTO or stainless (steel) wire SSM) be immersed in colloid
About 1 h in solution C takes out, is put into baking oven, 60 DEG C of 6 h of drying.By above-mentioned impregnated carbon cloth, (CC or carbon paper CP are led again
Electric glass FTO or stainless (steel) wire SSM) it is transferred in semiclosed porcelain boat, it is then transferred in temperature programming tube furnace, in Ar gas shielded
Under, temperature programming tube furnace is heated to keep the temperature 1 h after 400 DEG C with the heating rate of 10 DEG C/min, after naturally cool to room temperature
Afterwards, it takes out.
Embodiment 3
The preparation of iron-carbon (Fe-C) electrode is using dipping-calcining method: 0.1 g tannic acid is weighed in 50 mL beakers,
5 mL ethanol solutions are added thereto, magnetic agitation to Quan Rong forms solution A；It weighs 0.1 g Fe(NO3)39H2O and is dissolved in 5 mL
Solution B is formed in ethanol solution；Gained clear solution B is slowly added drop-wise in solution A, 2 h of room temperature magnetic agitation, forms colloid
Solution C.Take about 1 × 2 cm of size2Carbon cloth (CC or carbon paper CP or electro-conductive glass FTO or stainless (steel) wire SSM) be immersed in colloid
About 1 h in solution C takes out, is put into baking oven, 60 DEG C of 6 h of drying.By above-mentioned impregnated carbon cloth, (CC or carbon paper CP are led again
Electric glass FTO or stainless (steel) wire SSM) it is transferred in semiclosed porcelain boat, it is then transferred in temperature programming tube furnace, in Ar gas shielded
Under, temperature programming tube furnace is heated to keep the temperature 1 h after 500 DEG C with the heating rate of 10 DEG C/min, after naturally cool to room temperature
Afterwards, it takes out.
Embodiment 4
The preparation of iron-carbon (Fe-C) electrode is using dipping-calcining method: 1 g tannic acid is weighed in 50 mL beakers, to
10 mL ethanol solutions are wherein added, magnetic agitation to Quan Rong forms solution A；It weighs 0.5 g Fe(NO3)39H2O and is dissolved in 10 mL
Solution B is formed in ethanol solution；Gained clear solution B is slowly added drop-wise in solution A, 2 h of room temperature magnetic agitation, forms colloid
Solution C.Take about 1 × 2 cm of size2Carbon cloth (CC or carbon paper CP or electro-conductive glass FTO or stainless (steel) wire SSM) be immersed in colloid
About 1 h in solution C takes out, is put into baking oven, 60 DEG C of 6 h of drying.By above-mentioned impregnated carbon cloth, (CC or carbon paper CP are led again
Electric glass FTO or stainless (steel) wire SSM) it is transferred in semiclosed porcelain boat, it is then transferred in temperature programming tube furnace, in Ar gas shielded
Under, temperature programming tube furnace is heated to keep the temperature 1 h after 350 DEG C with the heating rate of 10 DEG C/min, after naturally cool to room temperature
Afterwards, it takes out.
Embodiment 5
The preparation of iron-carbon (Fe-C) electrode is using dipping-calcining method: 1 g tannic acid is weighed in 50 mL beakers, to
10 mL ethanol solutions are wherein added, magnetic agitation to Quan Rong forms solution A；It weighs 0.5 g Fe(NO3)39H2O and is dissolved in 10 mL
Solution B is formed in ethanol solution；Gained clear solution B is slowly added drop-wise in solution A, 2 h of room temperature magnetic agitation, forms colloid
Solution C.Take about 1 × 2 cm of size2Carbon cloth (CC or carbon paper CP or electro-conductive glass FTO or stainless (steel) wire SSM) be immersed in colloid
About 1 h in solution C takes out, is put into baking oven, 60 DEG C of 6 h of drying.By above-mentioned impregnated carbon cloth, (CC or carbon paper CP are led again
Electric glass FTO or stainless (steel) wire SSM) it is transferred in semiclosed porcelain boat, it is then transferred in temperature programming tube furnace, in Ar gas shielded
Under, temperature programming tube furnace is heated to keep the temperature 1 h after 400 DEG C with the heating rate of 10 DEG C/min, after naturally cool to room temperature
Afterwards, it takes out.
Embodiment 6
The preparation of iron-carbon (Fe-C) electrode is using dipping-calcining method: 1 g tannic acid is weighed in 50 mL beakers, to
10 mL ethanol solutions are wherein added, magnetic agitation to Quan Rong forms solution A；It weighs 0.5 g Fe(NO3)39H2O and is dissolved in 10 mL
Solution B is formed in ethanol solution；Gained clear solution B is slowly added drop-wise in solution A, 2 h of room temperature magnetic agitation, forms colloid
Solution C.Take about 1 × 2 cm of size2Carbon cloth (CC or carbon paper CP or electro-conductive glass FTO or stainless (steel) wire SSM) be immersed in colloid
About 1 h in solution C takes out, is put into baking oven, 60 DEG C of 6 h of drying.By above-mentioned impregnated carbon cloth, (CC or carbon paper CP are led again
Electric glass FTO or stainless (steel) wire SSM) it is transferred in semiclosed porcelain boat, it is then transferred in temperature programming tube furnace, in Ar gas shielded
Under, temperature programming tube furnace is heated to keep the temperature 1 h after 500 DEG C with the heating rate of 10 DEG C/min, after naturally cool to room temperature
Afterwards, it takes out.
Embodiment 7
The preparation of iron-carbon (Fe-C) electrode is using dipping-calcining method: 20 g tannic acids are weighed in 50 mL beakers, to
10 mL ethanol solutions are wherein added, magnetic agitation to Quan Rong forms solution A；It weighs 1 g Fe(NO3)39H2O and is dissolved in 20 mL second
Solution B is formed in alcoholic solution；Gained clear solution B is slowly added drop-wise in solution A, 2 h of room temperature magnetic agitation, it is molten to form colloid
Liquid C.Take about 1 × 2 cm of size2Carbon cloth (CC or carbon paper CP or electro-conductive glass FTO or stainless (steel) wire SSM) to be immersed in colloid molten
About 1 h in liquid C takes out, is put into baking oven, 60 DEG C of 6 h of drying.Again by above-mentioned impregnated carbon cloth (CC or carbon paper CP or conduction
Glass FTO or stainless (steel) wire SSM) it is transferred in semiclosed porcelain boat, it is then transferred in temperature programming tube furnace, in Ar gas shielded
Under, temperature programming tube furnace is heated to keep the temperature 1 h after 350 DEG C with the heating rate of 10 DEG C/min, after naturally cool to room temperature
Afterwards, it takes out.
Embodiment 8
The preparation of iron-carbon (Fe-C) electrode is using dipping-calcining method: 20 g tannic acids are weighed in 50 mL beakers, to
10 mL ethanol solutions are wherein added, magnetic agitation to Quan Rong forms solution A；It weighs 1 g Fe(NO3)39H2O and is dissolved in 20 mL second
Solution B is formed in alcoholic solution；Gained clear solution B is slowly added drop-wise in solution A, 2 h of room temperature magnetic agitation, it is molten to form colloid
Liquid C.Take about 1 × 2 cm of size2Carbon cloth (CC or carbon paper CP or electro-conductive glass FTO or stainless (steel) wire SSM) to be immersed in colloid molten
About 1 h in liquid C takes out, is put into baking oven, 60 DEG C of 6 h of drying.Again by above-mentioned impregnated carbon cloth (CC or carbon paper CP or conduction
Glass FTO or stainless (steel) wire SSM) it is transferred in semiclosed porcelain boat, it is then transferred in temperature programming tube furnace, in Ar gas shielded
Under, temperature programming tube furnace is heated to keep the temperature 1 h after 400 DEG C with the heating rate of 10 DEG C/min, after naturally cool to room temperature
Afterwards, it takes out.
Embodiment 9
The preparation of iron-carbon (Fe-C) electrode is using dipping-calcining method: 20 g tannic acids are weighed in 50 mL beakers, to
10 mL ethanol solutions are wherein added, magnetic agitation to Quan Rong forms solution A；It weighs 1 g Fe(NO3)39H2O and is dissolved in 20 mL second
Solution B is formed in alcoholic solution；Gained clear solution B is slowly added drop-wise in solution A, 2 h of room temperature magnetic agitation, it is molten to form colloid
Liquid C.Take about 1 × 2 cm of size2Carbon cloth (CC or carbon paper CP or electro-conductive glass FTO or stainless (steel) wire SSM) to be immersed in colloid molten
About 1 h in liquid C takes out, is put into baking oven, 60 DEG C of 6 h of drying.Again by above-mentioned impregnated carbon cloth (CC or carbon paper CP or conduction
Glass FTO or stainless (steel) wire SSM) it is transferred in semiclosed porcelain boat, it is then transferred in temperature programming tube furnace, in Ar gas shielded
Under, temperature programming tube furnace is heated to keep the temperature 1 h after 500 DEG C with the heating rate of 10 DEG C/min, after naturally cool to room temperature
Afterwards, it takes out.
Embodiment 10
Monatomic iron-carbon-coating modifies nanometer nickel sulfide piece (Fe-C/NiS2NS) preparation of electrode is using dipping-calcining
Method:
(1) 1 g tannic acid is weighed in 50 mL beakers, 10 mL ethanol solutions are added thereto, and magnetic agitation to Quan Rong is formed molten
Liquid A；It weighs 0.2 g Fe(NO3)39H2O and is dissolved in 15 mL ethanol solutions and form solution B；Gained clear solution B is slowly added dropwise
Into solution A, 2 h of room temperature magnetic agitation forms colloidal solution C.
(2) preparation Ni (OH) is improved according to document2Nanometer sheet (Xiao Ma, Min Ma, Danni Liu, Shuai
Hao, Fengli Qu, Gu Du, Abdullah M. Asiri, and Xuping Sun*, Core/Shell
Structured NiS2@Ni-Bi Nanoarray for Efficient Water Oxidation at Near-Neutral
pH, Chemcatchem, 2017, 9: 3138-3143.): weigh 0.5814 g of Nickelous nitrate hexahydrate, 0.148 g of ammonium fluoride
It is dissolved in 35 mL deionized waters with 0.6 g of urea, takes about 1 × 2 cm of size2Carbon cloth (CC or carbon paper CP or electro-conductive glass FTO or
Stainless (steel) wire SSM) it is put into above-mentioned solution system, it is transferred in 50 mL polytetrafluoroethylliner liner reaction kettles in 120 °C of baking ovens
6 h are reacted, are taken out after cooling, washing alcohol is washed several times, is put into baking oven, 60 DEG C of 6 h of drying obtain Ni (OH)2/ CC(or Ni
(OH)2/ CP or Ni (OH)2/ FTO or Ni (OH)2/ SSM).
(3) by Ni (OH)2/ CC(or Ni (OH)2/ CP or Ni (OH)2/ FTO or Ni (OH)2/ SSM) it is immersed in colloidal solution C
Middle about 1 h obtains Fe-G/Ni (OH)2/ CC(or Fe-G/Ni (OH)2/ CP or Fe-G/Ni (OH)2/ FTO or Fe-G/Ni (OH)2/
SSM), take out, be put into baking oven, 60 DEG C of 6 h of drying.0.1 g sulphur powder is weighed, is transferred in semi-enclosed porcelain boat, then by above-mentioned leaching
The good Fe-G/Ni of stain (OH)2/ CC(or Fe-G/Ni (OH)2/ CP or Fe-G/Ni (OH)2/ FTO or Fe-G/Ni (OH)2/ SSM) turn
Enter in porcelain boat, be then transferred in temperature programming tube furnace, under Ar gas shielded, by temperature programming tube furnace with 10 DEG C/min
Heating rate be heated to 350 DEG C after keep the temperature 2 h, after room temperature, take out.
Embodiment 11
Monatomic iron-carbon-coating modifies nanometer nickel sulfide piece (Fe-C/NiS2NS) preparation of electrode is using dipping-calcining
Method:
(1) 1 g tannic acid is weighed in 50 mL beakers, 10 mL ethanol solutions are added thereto, and magnetic agitation to Quan Rong is formed molten
Liquid A；It weighs 0.2 g Fe(NO3)39H2O and is dissolved in 15 mL ethanol solutions and form solution B；Gained clear solution B is slowly added dropwise
Into solution A, 2 h of room temperature magnetic agitation forms colloidal solution C.
(2) preparation Ni (OH) is improved according to document2Nanometer sheet (Xiao Ma, Min Ma, Danni Liu, Shuai
Hao, Fengli Qu, Gu Du, Abdullah M. Asiri, and Xuping Sun*, Core/Shell
Structured NiS2@Ni-Bi Nanoarray for Efficient Water Oxidation at Near-Neutral
pH, Chemcatchem, 2017, 9: 3138-3143.): weigh 0.5814 g of Nickelous nitrate hexahydrate, 0.148 g of ammonium fluoride
It is dissolved in 35 mL deionized waters with 0.6 g of urea, takes about 1 × 2 cm of size2Carbon cloth (CC or carbon paper CP or electro-conductive glass FTO or
Stainless (steel) wire SSM) it is put into above-mentioned solution system, it is transferred in 50 mL polytetrafluoroethylliner liner reaction kettles in 120 °C of baking ovens
6 h are reacted, are taken out after cooling, washing alcohol is washed several times, is put into baking oven, 60 DEG C of 6 h of drying obtain Ni (OH)2/ CC(or Ni
(OH)2/ CP or Ni (OH)2/ FTO or Ni (OH)2/ SSM).
(3) by Ni (OH)2/ CC(or Ni (OH)2/ CP or Ni (OH)2/ FTO or Ni (OH)2/ SSM) it is immersed in colloidal solution C
Middle about 1 h obtains Fe-G/Ni (OH)2/ CC(or Fe-G/Ni (OH)2/ CP or Fe-G/Ni (OH)2/ FTO or Fe-G/Ni (OH)2/
SSM), take out, be put into baking oven, 60 DEG C of 6 h of drying.0.1 g sulphur powder is weighed, is transferred in semi-enclosed porcelain boat, then by above-mentioned leaching
The good Fe-G/Ni of stain (OH)2/ CC(or Fe-G/Ni (OH)2/ CP or Fe-G/Ni (OH)2/ FTO or Fe-G/Ni (OH)2/ SSM) turn
Enter in porcelain boat, be then transferred in temperature programming tube furnace, under Ar gas shielded, by temperature programming tube furnace with 10 DEG C/min
Heating rate be heated to 400 DEG C after keep the temperature 2 h, after room temperature, take out.
Embodiment 12
Monatomic iron-carbon-coating modifies nanometer nickel sulfide piece (Fe-C/NiS2NS) preparation of electrode is using dipping-calcining
Method:
(1) 1 g tannic acid is weighed in 50 mL beakers, 10 mL ethanol solutions are added thereto, and magnetic agitation to Quan Rong is formed molten
Liquid A；It weighs 0.2 g Fe(NO3)39H2O and is dissolved in 15 mL ethanol solutions and form solution B；Gained clear solution B is slowly added dropwise
Into solution A, 2 h of room temperature magnetic agitation forms colloidal solution C.
(2) preparation Ni (OH) is improved according to document2Nanometer sheet (Xiao Ma, Min Ma, Danni Liu, Shuai
Hao, Fengli Qu, Gu Du, Abdullah M. Asiri, and Xuping Sun*, Core/Shell
Structured NiS2@Ni-Bi Nanoarray for Efficient Water Oxidation at Near-Neutral
pH, Chemcatchem, 2017, 9: 3138-3143.): weigh 0.5814 g of Nickelous nitrate hexahydrate, 0.148 g of ammonium fluoride
It is dissolved in 35 mL deionized waters with 0.6 g of urea, takes about 1 × 2 cm of size2Carbon cloth (CC or carbon paper CP or electro-conductive glass FTO or
Stainless (steel) wire SSM) it is put into above-mentioned solution system, it is transferred in 50 mL polytetrafluoroethylliner liner reaction kettles in 120 °C of baking ovens
6 h are reacted, are taken out after cooling, washing alcohol is washed several times, is put into baking oven, 60 DEG C of 6 h of drying obtain Ni (OH)2/ CC(or Ni
(OH)2/ CP or Ni (OH)2/ FTO or Ni (OH)2/ SSM).
(3) by Ni (OH)2/ CC(or Ni (OH)2/ CP or Ni (OH)2/ FTO or Ni (OH)2/ SSM) it is immersed in colloidal solution C
Middle about 1 h obtains Fe-G/Ni (OH)2/ CC(or Fe-G/Ni (OH)2/ CP or Fe-G/Ni (OH)2/ FTO or Fe-G/Ni (OH)2/
SSM), take out, be put into baking oven, 60 DEG C of 6 h of drying.0.1 g sulphur powder is weighed, is transferred in semi-enclosed porcelain boat, then by above-mentioned leaching
The good Fe-G/Ni of stain (OH)2/ CC(or Fe-G/Ni (OH)2/ CP or Fe-G/Ni (OH)2/ FTO or Fe-G/Ni (OH)2/ SSM) turn
Enter in porcelain boat, be then transferred in temperature programming tube furnace, under Ar gas shielded, by temperature programming tube furnace with 10 DEG C/min
Heating rate be heated to 500 DEG C after keep the temperature 2 h, after room temperature, take out.
Embodiment 13
Monatomic iron-carbon-coating modification vulcanization cobalt nanowire (Fe-C/CoS2NW) preparation of electrode is using dipping-calcining
Method:
(1) 1 g tannic acid is weighed in 50 mL beakers, 10 mL ethanol solutions are added thereto, and magnetic agitation to Quan Rong is formed molten
Liquid A；It weighs 0.2 g Fe(NO3)39H2O and is dissolved in 15 mL ethanol solutions and form solution B；Gained clear solution B is slowly added dropwise
Into solution A, 2 h of room temperature magnetic agitation forms colloidal solution C.
(2) according to document improve preparation Co (OH) F nano wire (Matthew S. Faber, Rafal Dziedzic,
Mark A. Lukowski, Nicholas S. Kaiser, Qi Ding, and Song Jin*, High-
performance electrocatalysis using metallic cobalt pyrite (CoS(2)) micro- and
nanostructures, J Am Chem Soc, 2014,136:10053-10061.): weigh cabaltous nitrate hexahydrate
0.5812 g, 0.147 g of ammonium fluoride and 0.6 g of urea are dissolved in 35 mL deionized waters, take about 1 × 2 cm of size2Carbon cloth (CC
Or carbon paper CP or electro-conductive glass FTO or stainless (steel) wire SSM) be put into above-mentioned solution system, it is transferred to 50 mL polytetrafluoroethylliner liners
6 h are reacted in 120 °C of baking ovens in reaction kettle, are taken out after cooling, washing alcohol is washed several times, is put into baking oven, 60 DEG C of dryings
6 h obtain Co (OH) F/CC(or Co (OH) F/CP or Co (OH) F/FTO or Co (OH) F/SSM).
(3) Co (OH) F/CC(or Co (OH) F/CP or Co (OH) F/FTO or Co (OH) F/SSM) is immersed in colloidal solution
About 1 h obtains Fe-G/Co (OH) F/CC(or Fe-G/Co (OH) F/CP or Fe-G/Co (OH) F/FTO or Fe-G/Co (OH) in C
F/SSM), take out, be put into baking oven, 60 DEG C of 6 h of drying.0.1 g sulphur powder is weighed, is transferred in semi-enclosed porcelain boat, then will be above-mentioned
Impregnated Fe-G/Co (OH) F/CC(or Fe-G/Co (OH) F/CP or Fe-G/Co (OH) F/FTO or Fe-G/Co (OH) F/
SSM it) is transferred in porcelain boat, is then transferred in temperature programming tube furnace, under Ar gas shielded, by temperature programming tube furnace with 10
DEG C/heating rate of min keeps the temperature 2 h after being heated to 350 DEG C, after room temperature, take out.
Embodiment 14
Monatomic iron-carbon-coating modification vulcanization cobalt nanowire (Fe-C/CoS2NW) preparation of electrode is using dipping-calcining
Method:
(1) 1 g tannic acid is weighed in 50 mL beakers, 10 mL ethanol solutions are added thereto, and magnetic agitation to Quan Rong is formed molten
Liquid A；It weighs 0.2 g Fe(NO3)39H2O and is dissolved in 15 mL ethanol solutions and form solution B；Gained clear solution B is slowly added dropwise
Into solution A, 2 h of room temperature magnetic agitation forms colloidal solution C.
(2) according to document improve preparation Co (OH) F nano wire (Matthew S. Faber, Rafal Dziedzic,
Mark A. Lukowski, Nicholas S. Kaiser, Qi Ding, and Song Jin*, High-
performance electrocatalysis using metallic cobalt pyrite (CoS(2)) micro- and
nanostructures, J Am Chem Soc, 2014,136:10053-10061.): weigh cabaltous nitrate hexahydrate
0.5812 g, 0.147 g of ammonium fluoride and 0.6 g of urea are dissolved in 35 mL deionized waters, take about 1 × 2 cm of size2Carbon cloth (CC
Or carbon paper CP or electro-conductive glass FTO or stainless (steel) wire SSM) be put into above-mentioned solution system, it is transferred to 50 mL polytetrafluoroethylliner liners
6 h are reacted in 120 °C of baking ovens in reaction kettle, are taken out after cooling, washing alcohol is washed several times, is put into baking oven, 60 DEG C of dryings
6 h obtain Co (OH) F/CC(or Co (OH) F/CP or Co (OH) F/FTO or Co (OH) F/SSM).
(3) Co (OH) F/CC(or Co (OH) F/CP or Co (OH) F/FTO or Co (OH) F/SSM) is immersed in colloidal solution
About 1 h obtains Fe-G/Co (OH) F/CC(or Fe-G/Co (OH) F/CP or Fe-G/Co (OH) F/FTO or Fe-G/Co (OH) in C
F/SSM), take out, be put into baking oven, 60 DEG C of 6 h of drying.0.1 g sulphur powder is weighed, is transferred in semi-enclosed porcelain boat, then will be above-mentioned
Impregnated Fe-G/Co (OH) F/CC(or Fe-G/Co (OH) F/CP or Fe-G/Co (OH) F/FTO or Fe-G/Co (OH) F/
SSM it) is transferred in porcelain boat, is then transferred in temperature programming tube furnace, under Ar gas shielded, by temperature programming tube furnace with 10
DEG C/heating rate of min keeps the temperature 2 h after being heated to 400 DEG C, after room temperature, take out.
Embodiment 15
Monatomic iron-carbon-coating modification vulcanization cobalt nanowire (Fe-C/CoS2NW) preparation of electrode is using dipping-calcining
Method:
(1) 1 g tannic acid is weighed in 50 mL beakers, 10 mL ethanol solutions are added thereto, and magnetic agitation to Quan Rong is formed molten
Liquid A；It weighs 0.2 g Fe(NO3)39H2O and is dissolved in 15 mL ethanol solutions and form solution B；Gained clear solution B is slowly added dropwise
Into solution A, 2 h of room temperature magnetic agitation forms colloidal solution C.
(2) according to document improve preparation Co (OH) F nano wire (Matthew S. Faber, Rafal Dziedzic,
Mark A. Lukowski, Nicholas S. Kaiser, Qi Ding, and Song Jin*, High-
performance electrocatalysis using metallic cobalt pyrite (CoS(2)) micro- and
nanostructures, J Am Chem Soc, 2014,136:10053-10061.): weigh cabaltous nitrate hexahydrate
0.5812 g, 0.147 g of ammonium fluoride and 0.6 g of urea are dissolved in 35 mL deionized waters, take about 1 × 2 cm of size2Carbon cloth (CC
Or carbon paper CP or electro-conductive glass FTO or stainless (steel) wire SSM) be put into above-mentioned solution system, it is transferred to 50 mL polytetrafluoroethylliner liners
6 h are reacted in 120 °C of baking ovens in reaction kettle, are taken out after cooling, washing alcohol is washed several times, is put into baking oven, 60 DEG C of dryings
6 h obtain Co (OH) F/CC(or Co (OH) F/CP or Co (OH) F/FTO or Co (OH) F/SSM).
(3) Co (OH) F/CC(or Co (OH) F/CP or Co (OH) F/FTO or Co (OH) F/SSM) is immersed in colloidal solution
About 1 h obtains Fe-G/Co (OH) F/CC(or Fe-G/Co (OH) F/CP or Fe-G/Co (OH) F/FTO or Fe-G/Co (OH) in C
F/SSM), take out, be put into baking oven, 60 DEG C of 6 h of drying.0.1 g sulphur powder is weighed, is transferred in semi-enclosed porcelain boat, then will be above-mentioned
Impregnated Fe-G/Co (OH) F/CC(or Fe-G/Co (OH) F/CP or Fe-G/Co (OH) F/FTO or Fe-G/Co (OH) F/
SSM it) is transferred in porcelain boat, is then transferred in temperature programming tube furnace, under Ar gas shielded, by temperature programming tube furnace with 10
DEG C/heating rate of min keeps the temperature 2 h after being heated to 500 DEG C, after room temperature, take out.
Embodiment 16
The preparation of monatomic iron-carbon-coating modification nickel oxide nano piece (Fe-C/NiO NS) electrode is using dipping-calcining side
Method:
(1) 1 g tannic acid is weighed in 50 mL beakers, 10 mL ethanol solutions are added thereto, and magnetic agitation to Quan Rong is formed molten
Liquid A；It weighs 0.2 g Fe(NO3)39H2O and is dissolved in 15 mL ethanol solutions and form solution B；Gained clear solution B is slowly added dropwise
Into solution A, 2 h of room temperature magnetic agitation forms colloidal solution C.
(2) preparation Ni (OH) is improved according to document2Nanometer sheet (Xiao Ma, Min Ma, Danni Liu, Shuai
Hao, Fengli Qu, Gu Du, Abdullah M. Asiri, and Xuping Sun*, Core/Shell
Structured NiS2@Ni-Bi Nanoarray for Efficient Water Oxidation at Near-Neutral
pH, Chemcatchem, 2017, 9: 3138-3143.): weigh 0.5814 g of Nickelous nitrate hexahydrate, 0.148 g of ammonium fluoride
It is dissolved in 35 mL deionized waters with 0.6 g of urea, takes about 1 × 2 cm of size2Carbon cloth (CC or carbon paper CP or electro-conductive glass FTO or
Stainless (steel) wire SSM) it is put into above-mentioned solution system, it is transferred in 50 mL polytetrafluoroethylliner liner reaction kettles in 120 °C of baking ovens
6 h are reacted, are taken out after cooling, washing alcohol is washed several times, is put into baking oven, 60 DEG C of 6 h of drying obtain Ni (OH)2/ CC(or Ni
(OH)2/ CP or Ni (OH)2/ FTO or Ni (OH)2/ SSM).
(3) by Ni (OH)2/ CC(or Ni (OH)2/ CP or Ni (OH)2/ FTO or Ni (OH)2/ SSM) it is immersed in colloidal solution C
Middle about 1 h obtains Fe-G/Ni (OH)2/ CC(or Fe-G/Ni (OH)2/ CP or Fe-G/Ni (OH)2/ FTO or Fe-G/Ni (OH)2/
SSM), take out, be put into baking oven, 60 DEG C of 6 h of drying.Again by above-mentioned impregnated Fe-G/Ni (OH)2/ CC(or Fe-G/Ni
(OH)2/ CP or Fe-G/Ni (OH)2/ FTO or Fe-G/Ni (OH)2/ SSM) it is transferred in semiclosed porcelain boat, it is then transferred to program liter
In warm tube furnace, under Ar gas shielded, protected after temperature programming tube furnace is heated to 350 DEG C with the heating rate of 10 DEG C/min
2 h of temperature take out after room temperature.
Embodiment 17
The preparation of monatomic iron-carbon-coating modification nickel oxide nano piece (Fe-C/NiO NS) electrode is using dipping-calcining side
Method:
(1) 1 g tannic acid is weighed in 50 mL beakers, 10 mL ethanol solutions are added thereto, and magnetic agitation to Quan Rong is formed molten
Liquid A；It weighs 0.2 g Fe(NO3)39H2O and is dissolved in 15 mL ethanol solutions and form solution B；Gained clear solution B is slowly added dropwise
Into solution A, 2 h of room temperature magnetic agitation forms colloidal solution C.
(2) preparation Ni (OH) is improved according to document2Nanometer sheet (Xiao Ma, Min Ma, Danni Liu, Shuai
Hao, Fengli Qu, Gu Du, Abdullah M. Asiri, and Xuping Sun*, Core/Shell
Structured NiS2@Ni-Bi Nanoarray for Efficient Water Oxidation at Near-Neutral
pH, Chemcatchem, 2017, 9: 3138-3143.): weigh 0.5814 g of Nickelous nitrate hexahydrate, 0.148 g of ammonium fluoride
It is dissolved in 35 mL deionized waters with 0.6 g of urea, takes about 1 × 2 cm of size2Carbon cloth (CC or carbon paper CP or electro-conductive glass FTO or
Stainless (steel) wire SSM) it is put into above-mentioned solution system, it is transferred in 50 mL polytetrafluoroethylliner liner reaction kettles in 120 °C of baking ovens
6 h are reacted, are taken out after cooling, washing alcohol is washed several times, is put into baking oven, 60 DEG C of 6 h of drying obtain Ni (OH)2/ CC(or Ni
(OH)2/ CP or Ni (OH)2/ FTO or Ni (OH)2/ SSM).
(3) by Ni (OH)2/ CC(or Ni (OH)2/ CP or Ni (OH)2/ FTO or Ni (OH)2/ SSM) it is immersed in colloidal solution C
Middle about 1 h obtains Fe-G/Ni (OH)2/ CC(or Fe-G/Ni (OH)2/ CP or Fe-G/Ni (OH)2/ FTO or Fe-G/Ni (OH)2/
SSM), take out, be put into baking oven, 60 DEG C of 6 h of drying.Again by above-mentioned impregnated Fe-G/Ni (OH)2/ CC(or Fe-G/Ni
(OH)2/ CP or Fe-G/Ni (OH)2/ FTO or Fe-G/Ni (OH)2/ SSM) it is transferred in semiclosed porcelain boat, it is then transferred to program liter
In warm tube furnace, under Ar gas shielded, protected after temperature programming tube furnace is heated to 400 DEG C with the heating rate of 10 DEG C/min
2 h of temperature take out after room temperature.
Embodiment 18
The preparation of monatomic iron-carbon-coating modification nickel oxide nano piece (Fe-C/NiO NS) electrode is using dipping-calcining side
Method:
(1) 1 g tannic acid is weighed in 50 mL beakers, 10 mL ethanol solutions are added thereto, and magnetic agitation to Quan Rong is formed molten
Liquid A；It weighs 0.2 g Fe(NO3)39H2O and is dissolved in 15 mL ethanol solutions and form solution B；Gained clear solution B is slowly added dropwise
Into solution A, 2 h of room temperature magnetic agitation forms colloidal solution C.
(2) preparation Ni (OH) is improved according to document2Nanometer sheet (Xiao Ma, Min Ma, Danni Liu, Shuai
Hao, Fengli Qu, Gu Du, Abdullah M. Asiri, and Xuping Sun*, Core/Shell
Structured NiS2@Ni-Bi Nanoarray for Efficient Water Oxidation at Near-Neutral
pH, Chemcatchem, 2017, 9: 3138-3143.): weigh 0.5814 g of Nickelous nitrate hexahydrate, 0.148 g of ammonium fluoride
It is dissolved in 35 mL deionized waters with 0.6 g of urea, takes about 1 × 2 cm of size2Carbon cloth (CC or carbon paper CP or electro-conductive glass FTO or
Stainless (steel) wire SSM) it is put into above-mentioned solution system, it is transferred in 50 mL polytetrafluoroethylliner liner reaction kettles in 120 °C of baking ovens
6 h are reacted, are taken out after cooling, washing alcohol is washed several times, is put into baking oven, 60 DEG C of 6 h of drying obtain Ni (OH)2/ CC(or Ni
(OH)2/ CP or Ni (OH)2/ FTO or Ni (OH)2/ SSM).
(3) by Ni (OH)2/ CC(or Ni (OH)2/ CP or Ni (OH)2/ FTO or Ni (OH)2/ SSM) it is immersed in colloidal solution C
Middle about 1 h obtains Fe-G/Ni (OH)2/ CC(or Fe-G/Ni (OH)2/ CP or Fe-G/Ni (OH)2/ FTO or Fe-G/Ni (OH)2/
SSM), take out, be put into baking oven, 60 DEG C of 6 h of drying.Again by above-mentioned impregnated Fe-G/Ni (OH)2/ CC(or Fe-G/Ni
(OH)2/ CP or Fe-G/Ni (OH)2/ FTO or Fe-G/Ni (OH)2/ SSM) it is transferred in semiclosed porcelain boat, it is then transferred to program liter
In warm tube furnace, under Ar gas shielded, protected after temperature programming tube furnace is heated to 500 DEG C with the heating rate of 10 DEG C/min
2 h of temperature take out after room temperature.
Embodiment 19
Monatomic iron-carbon-coating modifies nickel sulfide nanoparticles (Fe-C/NiS2NP) preparation of electrode is using dipping-calcining
Method:
(1) 1 g tannic acid is weighed in 50 mL beakers, 10 mL ethanol solutions are added thereto, and magnetic agitation to Quan Rong is formed molten
Liquid A；It weighs 0.2 g Fe(NO3)39H2O and is dissolved in 15 mL ethanol solutions and form solution B；Gained clear solution B is slowly added dropwise
Into solution A, 2 h of room temperature magnetic agitation forms colloidal solution C.
(2) preparation Ni (OH) is improved according to document2Nano particle (Lihong Dong, Ying Chu, and Wendong
Sun, Controllable synthesis of nickel hydroxide and porous nickel oxide
nanostructures with different morphologies, Chemistry, 2008,14:5064-5072.):
It weighs 0.6571 g of six hydration nickel sulfate and 0.132 g of sodium hydroxide is dissolved in 35 mL deionized waters, take about 1 × 2 cm of size2
Carbon cloth (CC or carbon paper CP or electro-conductive glass FTO or stainless (steel) wire SSM) be put into above-mentioned solution system, be transferred to 50 mL poly- four
24 h are reacted in 120 °C of baking ovens in vinyl fluoride liner reaction kettle, are taken out after cooling, washing alcohol is washed several times, and baking oven is put into
In, 60 DEG C of 6 h of drying obtain Ni (OH)2/ CC(or Ni (OH)2/ CP or Ni (OH)2/ FTO or Ni (OH)2/ SSM).
(3) by Ni (OH)2/ CC(or Ni (OH)2/ CP or Ni (OH)2/ FTO or Ni (OH)2/ SSM) it is immersed in colloidal solution C
Middle about 1 h obtains Fe-G/Ni (OH)2/ CC(or Fe-G/Ni (OH)2/ CP or Fe-G/Ni (OH)2/ FTO or Fe-G/Ni (OH)2/
SSM), take out, be put into baking oven, 60 DEG C of 6 h of drying.0.1 g sulphur powder is weighed, is transferred in semi-enclosed porcelain boat, then by above-mentioned leaching
The good Fe-G/Ni of stain (OH)2/ CC(or Fe-G/Ni (OH)2/ CP or Fe-G/Ni (OH)2/ FTO or Fe-G/Ni (OH)2/ SSM) turn
Enter in porcelain boat, be then transferred in temperature programming tube furnace, under Ar gas shielded, by temperature programming tube furnace with 10 DEG C/min
Heating rate be heated to 350 DEG C after keep the temperature 2 h, after room temperature, take out.
Embodiment 20
Monatomic iron-carbon-coating modifies nickel sulfide nanoparticles (Fe-C/NiS2NP) preparation of electrode is using dipping-calcining
Method:
(1) 1 g tannic acid is weighed in 50 mL beakers, 10 mL ethanol solutions are added thereto, and magnetic agitation to Quan Rong is formed molten
Liquid A；It weighs 0.2 g Fe(NO3)39H2O and is dissolved in 15 mL ethanol solutions and form solution B；Gained clear solution B is slowly added dropwise
Into solution A, 2 h of room temperature magnetic agitation forms colloidal solution C.
(2) preparation Ni (OH) is improved according to document2Nano particle (Lihong Dong, Ying Chu, and Wendong
Sun, Controllable synthesis of nickel hydroxide and porous nickel oxide
nanostructures with different morphologies, Chemistry, 2008,14:5064-5072.):
It weighs 0.6571 g of six hydration nickel sulfate and 0.132 g of sodium hydroxide is dissolved in 35 mL deionized waters, take about 1 × 2 cm of size2
Carbon cloth (CC or carbon paper CP or electro-conductive glass FTO or stainless (steel) wire SSM) be put into above-mentioned solution system, be transferred to 50 mL poly- four
24 h are reacted in 120 °C of baking ovens in vinyl fluoride liner reaction kettle, are taken out after cooling, washing alcohol is washed several times, and baking oven is put into
In, 60 DEG C of 6 h of drying obtain Ni (OH)2/ CC(or Ni (OH)2/ CP or Ni (OH)2/ FTO or Ni (OH)2/ SSM).
(3) by Ni (OH)2/ CC(or Ni (OH)2/ CP or Ni (OH)2/ FTO or Ni (OH)2/ SSM) it is immersed in colloidal solution C
Middle about 1 h obtains Fe-G/Ni (OH)2/ CC(or Fe-G/Ni (OH)2/ CP or Fe-G/Ni (OH)2/ FTO or Fe-G/Ni (OH)2/
SSM), take out, be put into baking oven, 60 DEG C of 6 h of drying.0.1 g sulphur powder is weighed, is transferred in semi-enclosed porcelain boat, then by above-mentioned leaching
The good Fe-G/Ni of stain (OH)2/ CC(or Fe-G/Ni (OH)2/ CP or Fe-G/Ni (OH)2/ FTO or Fe-G/Ni (OH)2/ SSM) turn
Enter in porcelain boat, be then transferred in temperature programming tube furnace, under Ar gas shielded, by temperature programming tube furnace with 10 DEG C/min
Heating rate be heated to 400 DEG C after keep the temperature 2 h, after room temperature, take out.
Embodiment 21
Monatomic iron-carbon-coating modifies nickel sulfide nanoparticles (Fe-C/NiS2NP) preparation of electrode is using dipping-calcining
Method:
(1) 1 g tannic acid is weighed in 50 mL beakers, 10 mL ethanol solutions are added thereto, and magnetic agitation to Quan Rong is formed molten
Liquid A；It weighs 0.2 g Fe(NO3)39H2O and is dissolved in 15 mL ethanol solutions and form solution B；Gained clear solution B is slowly added dropwise
Into solution A, 2 h of room temperature magnetic agitation forms colloidal solution C.
(2) preparation Ni (OH) is improved according to document2Nano particle (Lihong Dong, Ying Chu, and Wendong
Sun, Controllable synthesis of nickel hydroxide and porous nickel oxide
nanostructures with different morphologies, Chemistry, 2008,14:5064-5072.):
It weighs 0.6571 g of six hydration nickel sulfate and 0.132 g of sodium hydroxide is dissolved in 35 mL deionized waters, take about 1 × 2 cm of size2
Carbon cloth (CC or carbon paper CP or electro-conductive glass FTO or stainless (steel) wire SSM) be put into above-mentioned solution system, be transferred to 50 mL poly- four
24 h are reacted in 120 °C of baking ovens in vinyl fluoride liner reaction kettle, are taken out after cooling, washing alcohol is washed several times, and baking oven is put into
In, 60 DEG C of 6 h of drying obtain Ni (OH)2/ CC(or Ni (OH)2/ CP or Ni (OH)2/ FTO or Ni (OH)2/ SSM).
(3) by Ni (OH)2/ CC(or Ni (OH)2/ CP or Ni (OH)2/ FTO or Ni (OH)2/ SSM) it is immersed in colloidal solution C
Middle about 1 h obtains Fe-G/Ni (OH)2/ CC(or Fe-G/Ni (OH)2/ CP or Fe-G/Ni (OH)2/ FTO or Fe-G/Ni (OH)2/
SSM), take out, be put into baking oven, 60 DEG C of 6 h of drying.0.1 g sulphur powder is weighed, is transferred in semi-enclosed porcelain boat, then by above-mentioned leaching
The good Fe-G/Ni of stain (OH)2/ CC(or Fe-G/Ni (OH)2/ CP or Fe-G/Ni (OH)2/ FTO or Fe-G/Ni (OH)2/ SSM) turn
Enter in porcelain boat, be then transferred in temperature programming tube furnace, under Ar gas shielded, by temperature programming tube furnace with 10 DEG C/min
Heating rate be heated to 500 DEG C after keep the temperature 2 h, after room temperature, take out.
Embodiment 22
The preparation of monatomic iron-carbon-coating modification phosphatization cobalt nanowire (Fe-C/CoP NW) electrode is using dipping-calcining side
Method:
(1) 1 g tannic acid is weighed in 50 mL beakers, 10 mL ethanol solutions are added thereto, and magnetic agitation to Quan Rong is formed molten
Liquid A；It weighs 0.2 g Fe(NO3)39H2O and is dissolved in 15 mL ethanol solutions and form solution B；Gained clear solution B is slowly added dropwise
Into solution A, 2 h of room temperature magnetic agitation forms colloidal solution C.
(2) according to document improve preparation Co (OH) F nano wire (Matthew S. Faber, Rafal Dziedzic,
Mark A. Lukowski, Nicholas S. Kaiser, Qi Ding, and Song Jin*, High-
performance electrocatalysis using metallic cobalt pyrite (CoS(2)) micro- and
nanostructures, J Am Chem Soc, 2014,136:10053-10061.): weigh cabaltous nitrate hexahydrate
0.5812 g, 0.147 g of ammonium fluoride and 0.6 g of urea are dissolved in 35 mL deionized waters, take about 1 × 2 cm of size2Carbon cloth (CC
Or carbon paper CP or electro-conductive glass FTO or stainless (steel) wire SSM) be put into above-mentioned solution system, it is transferred to 50 mL polytetrafluoroethylliner liners
6 h are reacted in 120 °C of baking ovens in reaction kettle, are taken out after cooling, washing alcohol is washed several times, is put into baking oven, 60 DEG C of dryings
6 h obtain Co (OH) F/CC(or Co (OH) F/CP or Co (OH) F/FTO or Co (OH) F/SSM).
(3) Co (OH) F/CC(or Co (OH) F/CP or Co (OH) F/FTO or Co (OH) F/SSM) is immersed in colloidal solution
About 1 h obtains Fe-G/Co (OH) F/CC(or Fe-G/Co (OH) F/CP or Fe-G/Co (OH) F/FTO or Fe-G/Co (OH) in C
F/SSM), take out, be put into baking oven, 60 DEG C of 6 h of drying.1 g sodium hypophosphite is weighed, is transferred in semi-enclosed porcelain boat, then will
Above-mentioned impregnated Fe-G/Co (OH) F/CC(or Fe-G/Co (OH) F/CP or Fe-G/Co (OH) F/FTO or Fe-G/Co (OH)
F/SSM it) is transferred in porcelain boat, is then transferred in temperature programming tube furnace, under Ar gas shielded, by temperature programming tube furnace with 10
DEG C/heating rate of min keeps the temperature 2 h after being heated to 300 DEG C, after room temperature, take out.
Embodiment 23
Monatomic iron-carbon-coating modification nitridation cobalt nanowire (Fe-C/Co4N NW) electrode preparation using dipping-calcining
Method:
(1) 1 g tannic acid is weighed in 50 mL beakers, 10 mL ethanol solutions are added thereto, and magnetic agitation to Quan Rong is formed molten
Liquid A；It weighs 0.2 g Fe(NO3)39H2O and is dissolved in 15 mL ethanol solutions and form solution B；Gained clear solution B is slowly added dropwise
Into solution A, 2 h of room temperature magnetic agitation forms colloidal solution C.
(2) according to document improve preparation Co (OH) F nano wire (Matthew S. Faber, Rafal Dziedzic,
Mark A. Lukowski, Nicholas S. Kaiser, Qi Ding, and Song Jin*, High-
performance electrocatalysis using metallic cobalt pyrite (CoS(2)) micro- and
nanostructures, J Am Chem Soc, 2014,136:10053-10061.): weigh cabaltous nitrate hexahydrate
0.5812 g, 0.147 g of ammonium fluoride and 0.6 g of urea are dissolved in 35 mL deionized waters, take about 1 × 2 cm of size2Carbon cloth (CC
Or carbon paper CP or electro-conductive glass FTO or stainless (steel) wire SSM) be put into above-mentioned solution system, it is transferred to 50 mL polytetrafluoroethylliner liners
6 h are reacted in 120 °C of baking ovens in reaction kettle, are taken out after cooling, washing alcohol is washed several times, is put into baking oven, 60 DEG C of dryings
6 h obtain Co (OH) F/CC(or Co (OH) F/CP or Co (OH) F/FTO or Co (OH) F/SSM).
(3) Co (OH) F/CC(or Co (OH) F/CP or Co (OH) F/FTO or Co (OH) F/SSM) is immersed in colloidal solution
About 1 h obtains Fe-G/Co (OH) F/CC(or Fe-G/Co (OH) F/CP or Fe-G/Co (OH) F/FTO or Fe-G/Co (OH) in C
F/SSM), take out, be put into baking oven, 60 DEG C of 6 h of drying.By above-mentioned impregnated Fe-G/Co (OH) F/CC(or Fe-G/Co
(OH) F/CP or Fe-G/Co (OH) F/FTO or Fe-G/Co (OH) F/SSM) it is transferred in porcelain boat, it is then transferred to temperature programming pipe
In formula furnace, in gas volume ratio Ar:NH3Under=10:1, temperature programming tube furnace is heated with the heating rate of 10 DEG C/min
2 h are kept the temperature after to 420 DEG C, after room temperature, are taken out.
The different Ni-based electro catalytic activities with cobalt-based composite electrocatalyst of monatomic Fe-C layers of modification are tested:
As can be seen from Figure 1 simple NiS2Nanometer sheet (NiS2NS) and it is monatomic Fe-C layers modification NiS2Nanometer sheet (Fe-C/
NiS2NS XRD spectrum) is mainly by NiS2Nanometer sheet and the diffraction maximum of carbon paper are constituted, and illustrate material to grow in carbon paper substrate
NiS2Based on nanometer sheet, no apparent Fe-C layers of peak occurs, and illustrates that Fe-C layers in composite material of content is lower.
As can be seen from Figure 2 NiS2Porous nano chip architecture is presented in nanometer sheet, after monatomic Fe-C layers modification
NiS2Nanometer sheet can preferably keep a nanometer chip architecture without obvious porous structure.
As can be seen from Figure 3 it can see apparent carbon-coating structure at composite material edge, can see on carbon-coating
Apparent Fe is monatomic, and it is NiS that bright lattice fringe is then corresponding2(200) crystal face of nanometer sheet, illustrates Fe-C layers monatomic
Modification is in NiS2Nanometer sheet surface.
The NiS of prepared monatomic Fe-C layers modification as seen from Figure 42Nanometer sheet, the CoS of monatomic Fe-C layers of modification2It receives
Rice noodles, the NiS of the NiO nanometer sheet of monatomic Fe-C layers of modification and monatomic Fe-C layers of modification2Nano-particles reinforcement electrode material
Show that more excellent electro-catalysis oxygen evolution activity, especially monatomic iron-carbon-coating modification nickel sulfide are received compared to simple material
It is 40 mA cm in current density when rice piece composite material is used as electrocatalytic decomposition water positive electrode-2When overpotential up to 280 mV.
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 (9)
1. a kind of monatomic iron-carbon-coating of immersion-type modifies Ni-based or cobalt-based composite electrode preparation method, which is characterized in that
Include the following steps:
A. tannic acid is added in ethyl alcohol the ratio for being the mL of 0.1~20 g:5~20 according to solid-to-liquid ratio, and stirring forms solution A；
Fe(NO3)39H2O is dissolved in ethyl alcohol and forms solution B by the ratio for being B. the mL of 0.1~20 g:5~20 according to solid-to-liquid ratio；
C. solution B is slowly added dropwise into solution A, stirring forms colloidal solution；
D. about 1 × 2 cm of size is taken2Ni-based or cobalt-based base material has been grown, 1~24 h in above-mentioned colloidal solution is immersed in,
It takes out, drying obtains presoma Fe-G/Ni-Sub or Fe-G/Co-Sub；
E. the presoma Fe-G/Ni-Sub or Fe-G/Co-Sub of drying are transferred in semi-enclosed porcelain boat, sulphur source or phosphorus source is added
Or nitrogen source, or other raw materials are not added, be then transferred in temperature programming tube furnace high-temperature calcination 0.5 under inert gas protection~
4h, preferably 1 h, after room temperature, take out to get.
2. the monatomic iron-carbon-coating of immersion-type modifies Ni-based or cobalt-based composite electrode preparation side according to claim 1
Method, it is characterised in that: solid-to-liquid ratio described in step A is 1 g:10 mL.
3. the monatomic iron-carbon-coating of immersion-type modifies Ni-based or cobalt-based composite electrode preparation side according to claim 1
Method, it is characterised in that: solid-to-liquid ratio described in step B is 0.2 g:10 mL.
4. the monatomic iron-carbon-coating of immersion-type modifies Ni-based or cobalt-based composite electrode preparation side according to claim 1
Method, it is characterised in that: it is in carbon paper CP, carbon cloth CC, electro-conductive glass that Ni-based or cobalt-based base material has been grown described in step D
Growth has the compound or simple substance of nickel or cobalt on FTO or stainless (steel) wire SSM；Wherein, the compound of the nickel or simple substance are hydrogen-oxygen
Change nickel, nickel oxide or amorphous nickel；The compound or simple substance of the cobalt are cobalt hydroxide, cobalt oxide or amorphous cobalt.
5. the monatomic iron-carbon-coating of immersion-type modifies Ni-based or cobalt-based composite electrode preparation side according to claim 1
Method, it is characterised in that: 6 h in above-mentioned colloidal solution are immersed in described in step D.
6. the monatomic iron-carbon-coating of immersion-type modifies Ni-based or cobalt-based composite electrode preparation side according to claim 1
Method, it is characterised in that: sulphur source described in step E is sulphur powder, sublimed sulfur or thiocarbamide；Phosphorus source be sodium hypophosphite, red phosphorus or
White phosphorus；The nitrogen source is ammonia, urea or melamine.
7. the monatomic iron-carbon-coating of immersion-type modifies Ni-based or cobalt-based composite electrode preparation side according to claim 1
Method, it is characterised in that: calcination temperature described in step E is 300~500 DEG C, and heating rate is 10 DEG C/min, the inert gas
For nitrogen or argon gas.
8. the monatomic iron of immersion-type that-7 any the methods are prepared according to claim 1-carbon-coating modifies Ni-based or cobalt-based
Composite electrode.
9. a kind of application of composite electrode as claimed in claim 8, it is characterised in that: be applied to electrocatalytic decomposition water
Positive electrode.
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