CN108179434B - A kind of preparation method and application of NiO/NiS/CN nano-hybrid material - Google Patents
A kind of preparation method and application of NiO/NiS/CN nano-hybrid material Download PDFInfo
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- CN108179434B CN108179434B CN201711475647.XA CN201711475647A CN108179434B CN 108179434 B CN108179434 B CN 108179434B CN 201711475647 A CN201711475647 A CN 201711475647A CN 108179434 B CN108179434 B CN 108179434B
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Abstract
The invention discloses a kind of preparation method and application of NiO/NiS/CN nano-hybrid material, belong to the technical fields such as nano material, metal organic complex nano material and catalysis.Preparation method is that sulfur-bearing and nitrogen imidazoles ylidene ligands are made using imidazoles -4- formaldehyde and L-Methionine, it is prepared into foamed nickel supported metal organic coordination polymer composite material with nickel foam redox self assembly, the composite material is calcined in air atmosphere, nickel oxide and the aza material of nickel sulfide nano particle doped carbon is made.The preparation method, raw materials used at low cost, preparation process is simple, and energy consumption of reaction is low, has prospects for commercial application.The hybrid material is used for catalytic electrolysis elutriation oxygen, there is good analysis oxygen electro catalytic activity and electrochemical stability.
Description
Technical field
The present invention relates to a kind of preparation method and application of NiO/NiS/CN nano-hybrid material, belong to nano material, gold
Belong to the technical fields such as organic cooperation polymer and catalysis.
Background technique
In the energy rare 21 century, it is most promising new to be considered substitute fossil fuels for the hydrogen of non-polluting renewable
One of energy.However, electro-catalysis overpotential for oxygen evolution excessively high in electrolysis water reaction process, seriously reduces its utilization rate of electrical,
Limit water electrolysis hydrogen production industrial expansion.Therefore, stable and efficient electro-catalysis oxygen-separating catalyst research and development, for mentioning
The utilization rate of electrical of height electrolysis water and wastewater industry has very important significance.
In the system much explored, iridium dioxide (IrO2) and ruthenic oxide (RuO2) it is considered most effective.However,
Their rare and expensive prices limit its actual application extensively, for this purpose, developing efficient, inexpensive and earth rich content
Base metal oxygen-separating catalyst, reduce analysis oxygen electric consumption become an opportunities and challenges.
Inexpensive, high activity transition elements oxide of mutually catalyst has prospects for commercial application；It is carbon-based or Heteroatom doping
Transition elements oxide of mutually composite catalyst is also the innovative selection of oxygen-separating catalyst.
In recent years, metal organic coordination polymer obtains in fields such as gas storage, separation, catalysis, identification and drug deliveries
Obtained and be widely applied, the diversity of periodic structure and structure, provide using its as precursor construct carbon or (and) gold
Belong to the unique advantage of based nano-material.Currently, derived from the research day of metal organic coordination polymer precursor or template function material
Benefit increases, for example, porous carbon, metal oxide, metal/carbon and metal oxide/carbon nanomaterial have been reported, it is constructed
Metal oxide has shown excellent property, but often adopt for efficient supercapacitor, lithium ion battery and hydrogen reduction etc.
Strategy is 600-800 DEG C of high temperature pyrolysis, the pyroprocess, and usually frame collapses and leads metal organic coordination polymer precursor
The nano-oxide generated is caused to reunite.
Summary of the invention
Technical assignment of the invention first is that in order to make up for the deficiencies of the prior art, a kind of nickel oxide is provided and nickel sulfide is received
The preparation method of the preparation method of the aza material of rice corpuscles doped carbon, this method is raw materials used at low cost, and preparation process is simple,
Energy consumption of reaction is low, has prospects for commercial application.
The two of technical assignment of the invention are to provide a kind of purposes of NiO/NiS/CN nano-hybrid material, i.e., this is miscellaneous
Change material and be electrolysed elutriation oxygen for efficient catalytic, which has good analysis oxygen electro catalytic activity and electrochemical stability.
Technical scheme is as follows:
1. a kind of preparation method of NiO/NiS/CN nano-hybrid material, preparation step are as follows:
(1) use imidazoles ylidene ligands HL and nickel foam Ni for raw material, redox self assembly prepares foamed nickel supported metal
Organic coordination polymer Ni@NiL composite material；
The imidazoles ylidene ligands HL, structural formula are as follows:
Imidazoles ylidene ligands HL the preparation method is as follows:
10 mmol imidazoles -4- formaldehyde are dissolved in 20-30 mL methanol；The L-Methionine of 10 mmol and 5 mmol sodium carbonate are molten
In 20-30 mL water；Two solution blendings, are heated to reflux 1h；Mixed liquor is rotated, 60 DEG C of dryings, imidazoles ylidene ligands HL is made,
Yield 92-95%；
(2) Ni@NiL composite material is calcined in air atmosphere, foamed nickel supported nickel oxide and nickel sulfide is made
The aza material of nanoparticle doped carbon, i.e. NiO/NiS/CN nano-hybrid material.
Use imidazoles ylidene ligands HL and nickel foam Ni for raw material in the step (1), redox self assembly prepares foam
Nickel load metal organic coordination polymer Ni@NiL composite material, steps are as follows:
1.0-1.5g imidazoles ylidene ligands HL is dissolved in 15-18 mL water, imidazoles ylidene ligands HL aqueous solution is made；
1.5-2.0 g potassium peroxydisulfate is dissolved in 15-20 mL water, persulfate aqueous solution is made；
After imidazoles ylidene ligands HL aqueous solution and persulfate aqueous solution are blended, the cm of 1.0 cm × 1.0 is activated into nickel foam
It is immersed in mixed liquor, ambient temperature overnight, after foam nickel composite material is taken out, respectively with water and ethanol washing 3 times, dry, system
Obtain foamed nickel supported metal-organic coordination polymer Ni@NiL composite material；
The activation nickel foam is nickel foam to be immersed in 10-15 mL, 10 in the dilute hydrochloric acid that mass fraction is 10%
Min is dry to be made with distilled water flushing 3 times.
Ni@NiL composite material is calcined in air atmosphere in the step (2), is that Ni@NiL composite material is placed in tubular type
In furnace, 250-300 DEG C is heated in air atmosphere, heating rate is 5 DEG C/min, and 250-300 DEG C of heat preservation 2h cools to room
NiO/NiS/CN nano-hybrid material is made in temperature.
2. application of the NiO/NiS/CN nano-hybrid material of preparation method preparation as described above as elctro-catalyst
Using three-electrode electro Chemical work station, the cmNiO/NiS/CN of 1.0 cm × 1.0 nano-hybrid material is as work electricity
Pole, Pt piece (mm × 0.1 of 5 mm × 5 mm) are to electrode, and Hg/HgO electrode is reference electrode, is tested using polarization curve
Method is that the aqueous energy of electrocatalytic decomposition is tested in 0.5 M KOH aqueous solution in electrolyte.
The NiO/NiS/CN nano-hybrid material electrocatalytic decomposition water, as current density, J=15 mA/cm2When, current potential is
1.32 V(vs RHE)；Tafel slope is 65 mV dec-1, illustrate that the material efficiently analyses oxygen catalytic activity；Use 30 h
Front and back, such material polarization curve do not find significantly to change, and show that catalyst is with good stability.
Beneficial technical effect of the invention:
1. the hybrid material that the present invention obtains is the foam of imidazoles ylidene ligands and nickel foam redox self assembly preparation
Nickel load metal-organic coordination polymer composite material, i.e. Ni@NiL composite material, the preparation are based on potassium peroxydisulfate and foam
The slow redox of nickel generates Ni(II) ion, ligand HL is in foam nickel surface and Ni(II) ion self assembly generation NiL coordination
Polymer, i.e., foamed nickel supported metal-organic coordination polymer composite material Ni@NiL composite material；The composite material is in air
Atmosphere 250-300 DEG C of heating pyrolysis, Ni(II) ion in-situ oxidation generates nickel oxide and nickel sulfide nano particle, and ligand pyrolysis generates
Carbon and nitrogen substrate；Preparation process simple process, simple and easy to control, product preparation efficiency is high, is easy to industrialize.
2. hybrid material of the present invention is that partial size exists for the nickel oxide and nickel sulfide nano particle uniform load of 40-50 nm
On porous carbon, nitrogen substrate, specific surface area is high, nickel oxide and nickel sulfide nano particle, porous carbon, nitrogen composition base
Material exposes more and different active sites, has played the collaboration of nickel oxide and nickel sulfide nano particle and porous substrate
Effect, so that oxygen is analysed in catalysis based on the composite material, high catalytic efficiency and stability is good.
Specific embodiment
The present invention will be further described below with reference to examples, but protection scope of the present invention is not only limited to implement
Example, professionals in the field change to made by technical solution of the present invention, are within the scope of protection of the invention interior.
Embodiment 1
1. a kind of preparation method of NiO/NiS/CN nano-hybrid material
(1) imidazoles ylidene ligands HL is prepared
10 mmol imidazoles -4- formaldehyde are dissolved in 20 mL methanol；The L-Methionine of 10 mmol and 5 mmol sodium carbonate are dissolved in 20
In mL water；Two solution blendings, are heated to reflux 1h；Mixed liquor is rotated, 60 DEG C of dryings, imidazoles ylidene ligands HL, yield 92% is made；
The imidazoles ylidene ligands HL, structural formula are as follows:
(2) use imidazoles ylidene ligands HL and nickel foam Ni for raw material, redox self assembly prepares foamed nickel supported metal
Organic coordination polymer Ni@NiL composite material
1.0g imidazoles ylidene ligands HL is dissolved in 15 mL water, imidazoles ylidene ligands HL aqueous solution is made；By 1.5 g potassium peroxydisulfates
15 mL water are dissolved in, persulfate aqueous solution is made；Nickel foam is immersed in 10 mL, mass fraction as in 10% dilute hydrochloric acid 10
Min is dry that activation nickel foam is made with distilled water flushing 3 times；Imidazoles ylidene ligands HL aqueous solution and persulfate aqueous solution are total to
After mixed, the cm of 1.0 cm × 1.0 activation nickel foam is immersed in mixed liquor, ambient temperature overnight takes out foam nickel composite material
Afterwards, foamed nickel supported metal-organic coordination polymer Ni@NiL composite wood is made with water and ethanol washing 3 times, dry respectively
Material；
(3) Ni@NiL composite material is placed in tube furnace, 250 DEG C is heated in air atmosphere, heating rate 5
DEG C/min, 250 DEG C of heat preservation 2h cool to room temperature, foamed nickel supported nickel oxide and nickel sulfide nano particle doped carbon azepine are made
Change material, i.e. NiO/NiS/CN nano-hybrid material.
Embodiment 2
1. a kind of preparation method of NiO/NiS/CN nano-hybrid material
(1) imidazoles ylidene ligands HL is prepared
10 mmol imidazoles -4- formaldehyde are dissolved in 30 mL methanol；The L-Methionine of 10 mmol and 5 mmol sodium carbonate are dissolved in 30
In mL water；Two solution blendings, are heated to reflux 1h；Mixed liquor is rotated, 60 DEG C of dryings, imidazoles ylidene ligands HL, yield 95% is made；
The imidazoles ylidene ligands HL, structural formula is the same as embodiment 1；
(2) use imidazoles ylidene ligands HL and nickel foam Ni for raw material, redox self assembly prepares foamed nickel supported metal
Organic coordination polymer Ni@NiL composite material
1.5g imidazoles ylidene ligands HL is dissolved in 18 mL water, imidazoles ylidene ligands HL aqueous solution is made；By 2.0 g potassium peroxydisulfates
20 mL water are dissolved in, persulfate aqueous solution is made；Nickel foam is immersed in 15 mL, mass fraction as in 10% dilute hydrochloric acid 10
Min is dry that activation nickel foam is made with distilled water flushing 3 times；Imidazoles ylidene ligands HL aqueous solution and persulfate aqueous solution are total to
After mixed, the cm of 1.0 cm × 1.0 activation nickel foam is immersed in mixed liquor, ambient temperature overnight takes out foam nickel composite material
Afterwards, foamed nickel supported metal-organic coordination polymer Ni@NiL composite wood is made with water and ethanol washing 3 times, dry respectively
Material；
(3) Ni@NiL composite material is placed in tube furnace, 300 DEG C is heated in air atmosphere, heating rate 5
DEG C/min, 300 DEG C of heat preservation 2h cool to room temperature, foamed nickel supported nickel oxide and nickel sulfide nano particle doped carbon azepine are made
Change material, i.e. NiO/NiS/CN nano-hybrid material.
Embodiment 3
1. a kind of preparation method of NiO/NiS/CN nano-hybrid material
(1) imidazoles ylidene ligands HL is prepared
10 mmol imidazoles -4- formaldehyde are dissolved in 27 mL methanol；The L-Methionine of 10 mmol and 5 mmol sodium carbonate are dissolved in 25
In mL water；Two solution blendings, are heated to reflux 1h；Mixed liquor is rotated, 60 DEG C of dryings, imidazoles ylidene ligands HL, yield 93% is made；
The imidazoles ylidene ligands HL, structural formula is the same as embodiment 1；
(2) use imidazoles ylidene ligands HL and nickel foam Ni for raw material, redox self assembly prepares foamed nickel supported metal
Organic coordination polymer Ni@NiL composite material
1.3g imidazoles ylidene ligands HL is dissolved in 17 mL water, imidazoles ylidene ligands HL aqueous solution is made；By 1.7 g potassium peroxydisulfates
17 mL water are dissolved in, persulfate aqueous solution is made；By the dilute hydrochloric acid that nickel foam is immersed in 10-15 mL, mass fraction is 10%
In 10 min, it is dry that activation nickel foam is made with distilled water flushing 3 times；By imidazoles ylidene ligands HL aqueous solution and potassium peroxydisulfate water
After solution blending, the cm of 1.0 cm × 1.0 activation nickel foam is immersed in mixed liquor, ambient temperature overnight, by foam nickel composite material
After taking-up, respectively with water and ethanol washing 3 times, dry, it is compound that foamed nickel supported metal-organic coordination polymer Ni@NiL is made
Material；
(3) Ni@NiL composite material is placed in tube furnace, 270 DEG C is heated in air atmosphere, heating rate 5
DEG C/min, 270 DEG C of heat preservation 2h cool to room temperature, foamed nickel supported nickel oxide and nickel sulfide nano particle doped carbon azepine are made
Change material, i.e. NiO/NiS/CN nano-hybrid material.
Embodiment 4
Embodiment 1, embodiment 2 or NiO/NiS/CN nano-hybrid material described in embodiment 3 are as electrochemical catalyst
Application: use three-electrode electro Chemical work station, the cm NiO/NiS/CN nano-hybrid material of 1.0 cm × 1.0 is electric as work
Pole, Pt piece (mm × 0.1 of 5 mm × 5 mm) are to electrode, and Hg/HgO electrode is reference electrode, is tested using polarization curve
Method is that the aqueous energy of electrocatalytic decomposition is tested in 0.5 M KOH aqueous solution in electrolyte；The NiO/NiS/CN nano hybridization material
Electrocatalytic decomposition water is expected, as current density, J=15 mA/cm2When, current potential is 1.32 V(vs RHE)；Tafel slope is 65 mV
dec-1, illustrate that the material efficiently analyses oxygen catalytic activity；Using before and after 30 h, such material polarization curve is not found obviously
Variation, show that catalyst is with good stability.
Claims (4)
1. a kind of preparation method of NiO/NiS/CN nano-hybrid material, which is characterized in that preparation step is as follows:
(1) 1.0-1.5g imidazoles ylidene ligands HL is dissolved in 15-18mL water, imidazoles ylidene ligands HL aqueous solution is made；
1.5-2.0g potassium peroxydisulfate is dissolved in 15-20mL water, persulfate aqueous solution is made；
After imidazoles ylidene ligands HL aqueous solution and persulfate aqueous solution are blended, 1.0cm × 1.0cm activation nickel foam is immersed in
In mixed liquor, after taking out foam nickel composite material, respectively with water and ethanol washing 3 times, dry, foam is made in ambient temperature overnight
Nickel load metal-organic coordination polymer Ni@NiL composite material；
The imidazoles ylidene ligands HL, structural formula are as follows:
Imidazoles ylidene ligands HL the preparation method is as follows:
10mmol imidazoles -4- formaldehyde is dissolved in 20-30mL methanol；The L-Methionine and 5mmol sodium carbonate of 10mmol is dissolved in 20-30mL
In water；Two solution blendings, are heated to reflux 1h；Mixed liquor is rotated, 60 DEG C of dryings, imidazoles ylidene ligands HL, yield 92- is made
95%；
(2) Ni@NiL composite material is calcined in air atmosphere, foamed nickel supported nickel oxide and nickel sulfide nano particle doping is made
The aza material of carbon, i.e. NiO/NiS/CN nano-hybrid material.
2. a kind of NiO/NiS/CN nano-hybrid material preparation method as described in claim 1, which is characterized in that the activation
Nickel foam is that nickel foam is immersed in 10-15mL, mass fraction for 10min in 10% dilute hydrochloric acid, with distilled water flushing 3 times,
It is dry to be made.
3. a kind of NiO/NiS/CN nano-hybrid material preparation method as described in claim 1, which is characterized in that described
Ni@NiL composite material is calcined in air atmosphere in step (2), is that Ni@NiL composite material is placed in tube furnace, in air atmosphere
It is heated to 250-300 DEG C, heating rate is 5 DEG C/min, and 250-300 DEG C of heat preservation 2h cools to room temperature, and NiO/NiS/ is made
CN nano-hybrid material.
4. NiO/NiS/CN nano-hybrid material the answering as elctro-catalyst of preparation method preparation as described in claim 1
With.
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| An efficient NiS@N/S-C hybrid oxygen evolution electrocatalyst derivedfrom metal-organic framework;Liu Yang;《Electrochimica Acta》;20160122;第191卷;全文 |
| Hierarchically Porous Ni3S2 Nanorod Array Foam as Highly EfficientElectrocatalyst for Hydrogen Evolution Reaction and Oxygen Evolution Reaction;Canbin Ouyang;《Electrochimica Acta》;20150601;第174卷;全文 |
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