CN108220997B - A kind of carbon containing nickel coat single-walled carbon nanotube composite material and preparation method and purposes - Google Patents
A kind of carbon containing nickel coat single-walled carbon nanotube composite material and preparation method and purposes Download PDFInfo
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Abstract
The invention belongs to energy catalysis material field, in particular to a kind of carbon containing nickel coat single-walled carbon nanotube composite material and preparation method and purposes.The present invention goes out the electrolysis water catalyst of carbon containing nickel coat single-walled carbon nanotube composite material by direct current arc method one-step synthesis, and whole process is easy to operation, and using graphite and nickel metal and alloy as primary raw material, low in cost, it is easy to accomplish prepare with scale；Obtained electrolysis water catalyst has natural porous network structure, and with single-walled carbon nanotube for main network frame, good conductivity is very beneficial for electron-transport and gas evolution in electrolysis water reaction process.Catalytic activity more preferably than industrial common iridium dioxide catalyst is shown using the material as anode of electrolytic water catalyst, while it also has catalytic activity for hydrogen evolution.
Description
Technical field
The invention belongs to energy catalysis material field, in particular to a kind of carbon containing nickel coat single-walled carbon nanotube composite material and
Preparation method and use.
Background technique
Energy shortage is facing challenges in human social process.Electrolysis water oxygen and hydrogen are to solve the energy
One effective way of shortage problem.However, the dynamic process of electro-catalysis oxygen evolution reaction is wanted during electrocatalytic decomposition water
Than evolving hydrogen reaction more slowly, the raising of water electrolysis efficiency is seriously hindered.Therefore, the efficient electrolysis elutriation oxygen catalysis of exploitation
Agent is the key that promote electrolysis water efficiency.Currently, industrial common electrolysis elutriation oxygen liberation of hydrogen catalyst iridium dioxide, titanium dioxide
Ruthenium or platinum dioxide are considered as that current industry is the most efficiently electrolysed elutriation oxygen liberation of hydrogen catalyst.However, these catalyst categories
Low in the reserves of the earth in rare metal, expensive, preparation cost is high, limits answering extensively for its industrialization significantly
With.In order to solve this technical bottleneck, some cheap base metal electrolysis water catalyst developed in recent years are closed by extensive
Note, such as sulfate, selenides, phosphide and other base metal complex chemical compounds.However, the method for preparing these materials
The process of complicated synthesis and purifying is generally comprised, not only process is cumbersome and time-consuming, is unfavorable for the popularization of extensive industrialization.
Summary of the invention
In view of the problems of the existing technology, the present invention provides a kind of carbon containing nickel coat single-walled carbon nanotube composite material and
Preparation method and use.
The technical scheme is that
A kind of carbon containing nickel coat single-walled carbon nanotube composite material, comprising single-walled carbon nanotube, is coated with nano metal nickel
Crystal form carbon particle and the agraphitic carbon for being coated with nano metal nickel, and it is interlaced between these types of carbon material ingredient, it is formed more
The reticular structure in hole.The nano metal nickel being wrapped by its having a size of 1~40nm.Nickel tenor is in catalyst material
9.5wt%~40wt%.It, which both can be used as Oxygen anodic evolution catalyst use, can also be used as the use of cathode hydrogen evolution catalyst.
A kind of preparation method of carbon containing nickel coat single-walled carbon nanotube composite material, comprising the following steps:
1) the pure graphite rod using diameter more than or equal to anode is as cathode, to urge mixed with nickel metal or nickel metal alloy
The graphite rod of agent and promotor is separately mounted in DC arc discharge room as anode, and by two ends in them
Yin-yang the two poles of the earth, and keep graphite rod other two end level in yin-yang the two poles of the earth opposite.
2) closed DC arc discharge room is vacuumized, is then passed through helium, helium toward DC arc discharge room again
The initial pressure of gas is maintained at 0.2bar~1bar.
3) discharge current is set as 60~120A, has started arc discharge between yin-yang the two poles of the earth after energization.In the electric discharge starting the arc
The spacing that two interpolar of yin-yang is kept in journey is 1~10mm, and graphite anode rod is constantly consumed until its current interruption that is exhausted, puts
Electric indoor netted black solid is the carbon containing nickel coat single-walled carbon nanotube composite material being prepared.
4) using the product of step 3) as raw material, in 280 DEG C~480 DEG C 0.1~12h of calcination or in concentration in air atmosphere
The part agraphitic carbon in raw material is removed for room temperature in the hydrogen peroxide of 5wt%~30wt% or return stirring 0.5~oxidation for 24 hours,
The carbon containing nickel coat carbon nano tube compound material after removal agraphitic carbon is obtained by the nickel oxide that acid solution dissolves surface again.
5) isopropanol and 5%Nafion solution are obtained into mixed solution according to volume ratio (10~20): 1, by step 3), 4)
Obtained black solid ultrasonic disperse is applied on foam nickel electrode into mixed solution, dry, obtains electrolysis elutriation oxygen electricity
Pole, the carrying capacity of catalyst are 0.8mg/cm2。
The purity of the graphite rod is greater than 99%.
The metallic nickel or metallic nickel alloy catalyst is one or both of metallic nickel or yttrium nickel alloy, catalyst
The content of middle nickel is 2at%~8at%, and the content refers to accounting for the total atom percentage of graphite.
The promotor is one of elemental sulfur, ferrous sulfide, iron sulfide, nickel sulfide or a variety of, sulphur in promotor
Content be 0~1at%.
The acid solution is one of hydrochloric acid, sulfuric acid, nitric acid or carboxylic acid or a variety of.
Step 3), step 4) product used as electrolysis water catalyst.
The invention has the benefit that
1) present invention has synthesized electrolysis water catalyst using graphite rod and metallic nickel or metallic nickel alloy as raw material, for
For noble metal catalyst, reduce costs.
2) present invention uses DC arc discharge one-step synthesis electrolysis water catalyst, and whole process is easy to operation,
Can prepare with scale, and atmosphere used be inert atmosphere, securely and reliably.
3) anode of electrolytic water catalyst of the invention has excellent catalytic activity to oxygen evolution reaction, and catalytic activity is bright
It is aobvious to be better than iridium dioxide catalytic activity.
4) electrolysis water catalyst of the invention can not only be used for anode catalyst, can also be used as cathod catalyst.
5) electrolysis water catalyst of the invention by single-walled carbon nanotube, be coated with nano metal nickel crystal form carbon particle and
It is coated with the agraphitic carbon composition of nano metal nickel, wherein the single defective tube of DC arc discharge synthesis lacks quality
High guiding performance is good, and is mutually wound reticular structure, is conducive to electronics conduction, and this porous network structure can be improved
Active area is also beneficial to the precipitation of oxygen.
Detailed description of the invention
Fig. 1 is the transmission electron microscope photo of carbon containing nickel coat single-walled carbon nanotube composite material prepared by embodiment 1.
Fig. 2 is the anode of electrolytic water polarization curve of the resulting material of embodiment 1.
Fig. 3 is the electrolysis water cathodic polarization curve of the resulting material of embodiment 1.
Fig. 4 is the transmission electron microscope photo of carbon containing nickel coat single-walled carbon nanotube composite material prepared by embodiment 2.
Fig. 5 is the transmission electron microscope photo of carbon containing nickel coat single-walled carbon nanotube composite material prepared by embodiment 3.
Fig. 6 is the transmission electron microscope photo of carbon containing nickel coat single-walled carbon nanotube composite material prepared by embodiment 4.
Fig. 7 is the transmission electron microscope photo of carbon containing nickel coat single-walled carbon nanotube composite material prepared by embodiment 5.
Fig. 8 is the transmission electron microscope photo of carbon containing nickel coat single-walled carbon nanotube composite material prepared by embodiment 8.
Fig. 9 is the polarization curve of the anode of electrolytic water of material prepared by embodiment 8.
Figure 10 is the polarization curve (curve E) of the electrolysis water cathode of material prepared by embodiment 8.
Specific embodiment
Embodiment 1:
1) preparation of carbon containing nickel coat single-walled carbon nanotube composite material:
Graphite powder (purity 99%), catalyst yttrium nickel alloy powder and promotor ferrous sulfide powder are mixed by a certain percentage
Close, and be compressed into diameter be 6mm stick, then using one end of which is fixed on the anode of the DC arc discharge room of sealing as
Graphite anode rod；Wherein, nickel element is 4.0at% relative to graphite total atom percentage, and element sulphur is relative to graphite total atom
Percentage 1at%.One end that another diameter is the pure graphite rod of 8mm is fixed on to the cathode of DC arc discharge room, keeps two
Two end levels of a graphite rod are opposite.DC arc discharge room is evacuated, and is filled with high-purity helium, keeps helium gas
The initial gas pressure of atmosphere is 0.7bar.Then direct-current discharge electric current is kept, 80A carries out the electric discharge starting the arc, keeps yin during discharge
The spacing of positive the two poles of the earth end is in 1~10mm, electric discharge stopping until graphite anode rod is exhausted, and entire discharge process about 5 minutes.
The netted black solid object generated in arc chamber is electrolysis water catalyst.
Fig. 1 is the transmission electron microscope photo of carbon containing nickel coat single-walled carbon nanotube composite material prepared by embodiment 1, the electrolysis
Water catalyst is a kind of nano carbon composite material, and it includes the crystal form carbon for having single-walled carbon nanotube, being coated with nano metal nickel
Grain and the agraphitic carbon for being coated with nano metal nickel.It is interlaced between single-walled carbon nanotube, form porous reticular structure；It is brilliant
Type carbon particle and metal nickel particle are then embedded in single walled carbon nanotube network.Wherein the size of nano metal nickel be 1~
40nm.The content of metallic nickel is 18.5wt%.
2) production of electrolysis water electrode:
Isopropanol and 5%Nafion solution are obtained into mixed solution according to volume ratio 20:1, the 10mg of above-mentioned preparation is contained
Carbon nickel coat single-walled carbon nanotube compound material ultrasound is distributed in the above-mentioned mixed solution of 5ml, then applies uniform dispersion liquid
It overlays on clean foam nickel electrode, it is dry, two electrodes of electrolysis water yin-yang are respectively obtained, the carrying capacity of catalyst is 0.8mg/
cm2.For the ease of comparing, using iridium dioxide as anode catalyst, anode of electrolytic water catalysis electricity is produced with same step
Pole.
3) the electrocatalysis characteristic test of electrolysis water catalyst:
It is that is saturated by Ag/AgCl normal electrode and is made for electrode with metal platinized platinum with the electrolytic water electric of production extremely working electrode
For reference electrode, the KOH solution of 1mol/L is electrolyte, forms a three electrode test systems, surveys respectively at normal temperatures and pressures
Examination obtains the polarization curve of polarization curve and electrolysis water liberation of hydrogen that electrolysis water oxygen is precipitated.Fig. 2 is the resulting electrolysis water of the present embodiment
The polarization curve of oxygen precipitation catalyst；Fig. 3 is the polarization curve of the resulting electrolysis water liberation of hydrogen catalyst of the present embodiment.This in Fig. 2
It plays spike potential as 1.55V (vs.RHE) to the electrolysis water oxygen-separating catalyst of invention, is better than IrO2Rise spike potential (1.56V
vs.RHE)；It is 50mA/cm in electrolytic current density2When, overpotential 390mV, hence it is evident that be better than IrO2440mV.Table in Fig. 3
Bright catalyst material of the invention the catalytic activity with oxygen evolution reaction simultaneously, also have catalytic activity for hydrogen evolution, in 60mA/
cm2When, overpotential of hydrogen evolution 329mV.
Embodiment 2:
2 difference from Example 1 of embodiment is in graphite anode rod, atomic percent of the nickel element relative to graphite
8at%, atomic percent 1at% of the element sulphur relative to graphite, the initial voltage of helium atmosphere are adjusted to 0.5bar, electric discharge electricity
Stream remains 60A；Entire discharge process is about 10 minutes, and it is the carbon containing nickel coat prepared that arc chamber, which obtains netted black solid object,
Single-walled carbon nanotube composite material, wherein nickel tenor is about 40wt%.
Fig. 4 is the transmission electron microscope photo of carbon containing nickel coat single-walled carbon nanotube composite material prepared by embodiment 2.
Embodiment 3:
3 difference from Example 1 of embodiment is in graphite anode rod that catalyst is changed to nickel powder, and promotor is changed to vulcanization
Nickel powder, atomic percent 2at% of the nickel element relative to graphite, atomic percent 1at% of the element sulphur relative to graphite, helium
The initial voltage of atmosphere is adjusted to 1bar, and discharge current remains 60A；Entire discharge process is about 10 minutes, and arc chamber is same
Netted black solid object is obtained, wherein the content of nickel metal is about 9.5wt%.
Fig. 5 is the transmission electron microscope photo of carbon containing nickel coat single-walled carbon nanotube composite material prepared by embodiment 3.
Embodiment 4:
4 difference from Example 1 of embodiment is in graphite anode rod that catalyst is changed to nickel powder, and promotor is changed to sulphur
Powder, atomic percent 4at% of the nickel element relative to graphite, atomic percent 1at% of the element sulphur relative to graphite, helium gas
The initial voltage of atmosphere is adjusted to 0.2bar, and discharge current remains 120A；Entire discharge process is about 3 minutes, and arc chamber is same
Netted black solid object is obtained, wherein the content of nickel metal is about 16.5wt%.
Fig. 6 is the transmission electron microscope photo of carbon containing nickel coat single-walled carbon nanotube composite material prepared by embodiment 4.
Embodiment 5:
5 difference from Example 1 of embodiment is not add promotor in graphite anode rod, and entire discharge process is about
5 minutes, arc chamber was similarly obtained netted black solid object.
Fig. 7 is the transmission electron microscope photo of carbon containing nickel coat single-walled carbon nanotube composite material prepared by embodiment 4.
Embodiment 6:
The product of embodiment 1 is first stirred at room temperature for 24 hours in 5wt% hydrogen peroxide, then the tube furnace again at 280 DEG C is hollow
Gas calcination 12h.The product after calcination is put into return stirring 3h in 2.6M nitric acid solution again, is just obtained through filtering, washing, drying
Product.
Embodiment 7:
The product of embodiment 1 is placed directly in tube furnace, is put into 480 DEG C of calcination 0.1h, then by the product after calcination
Return stirring 3h in 6M hydrochloric acid solution just obtains product through filtering, washing, drying.
Embodiment 8:
The product of embodiment 1 is put into the black solid object that return stirring 0.5h in 30wt% hydrogen peroxide is obtained by filtration to set
In tube furnace, it is put into return stirring 3h in 2.6M nitric acid solution in 400-450 DEG C of calcination 1h, then by the product after calcination, is passed through
Filtering, washing, drying just obtain product.By in embodiment 1,2), 3) step production electrode and electrocatalysis characteristic are tested again.In Fig. 9
It plays spike potential as 1.53V (vs.RHE) to electrolysis water oxygen-separating catalyst of the invention, is better than IrO2Rise spike potential (1.56V
vs.RHE)；It is 50mA/cm in electrolytic current density2When, overpotential 360mV, hence it is evident that be better than IrO2440mV.In Figure 10
Show catalyst material of the invention the catalytic activity with oxygen evolution reaction simultaneously, also have catalytic activity for hydrogen evolution,
60mA/cm2When, overpotential of hydrogen evolution 312mV.
Claims (7)
1. a kind of preparation method of carbon containing nickel coat single-walled carbon nanotube composite material, which is characterized in that prepared with direct current arc method
Carbon containing nickel coat single-walled carbon nanotube composite material, comprising the following steps:
Using the graphite rod mixed with metallic nickel or nickel metal alloy catalyst and promotor as anode, using pure graphite rod as cathode,
Yin-yang the two poles of the earth of closed arc discharge chamber are separately mounted to, the initial pressure for adjusting high-purity helium is 0.2~1bar, electric discharge
Electric current is that 60~120A has carried out arc discharge；The spacing that two interpolar of yin-yang is kept in electric discharge Igniting pattern is 1~10mm, anode
Graphite rod is constantly consumed up to black solid netted in its current interruption that is exhausted, arc chamber is carbon containing nickel coat single
Pipe composite material；The metallic nickel or metallic nickel alloy catalyst is one or both of metallic nickel or yttrium nickel alloy, is urged
The content of nickel is 2at%~8at% in agent, and the content refers to accounting for the total atom percentage of graphite；The conduct
The preparation method of the graphite rod of anode is to suppress and make by physics after mixing in proportion catalyst, promotor and graphite powder
At；
Using the composite material of above-mentioned preparation as raw material, room temperature or reflux in the hydrogen peroxide that concentration is 5wt%~30wt% in advance
Stirring 0.5~for 24 hours, then the part in raw materials is removed without fixed in 280 DEG C~480 DEG C 0.1~12h of calcination oxidation in air atmosphere
Type carbon, then the carbon containing nickel coat carbon nanotube composite after removal agraphitic carbon is obtained by the nickel oxide that acid solution dissolves surface
Material.
2. preparation method according to claim 1, which is characterized in that the purity of the graphite is more than or equal to 99%.
3. preparation method according to claim 1, which is characterized in that the promotor is elemental sulfur, ferrous sulfide, sulphur
Change one of iron, nickel sulfide or a variety of, the content of sulphur is 0~1at% in promotor.
4. preparation method according to claim 1, which is characterized in that the acid solution is hydrochloric acid, sulfuric acid, nitric acid or carboxylic
One of acid is a variety of.
5. a kind of nickel coat single-walled carbon nanotube composite material carbon containing as prepared by claim any one of 1-4, which is characterized in that
Comprising single-walled carbon nanotube, it is coated with the crystal form carbon particle of nano metal nickel and is coated with the agraphitic carbon of nano metal nickel；It is single
It is interlaced between wall carbon nano tube, porous reticular structure is formed, crystal form carbon particle and agraphitic carbon are embedded in single wall carbon and receive
Between the grid of mitron.
6. composite material according to claim 5, which is characterized in that the nano metal nickel particle size is 1~40nm,
Nickel tenor is 9.5wt%~40wt%.
7. the purposes of composite material described in claim 5, which is characterized in that the composite material is as anode of electrolytic water or yin
Electrode catalyst.
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| CN108940288B (en) * | 2018-07-27 | 2020-10-27 | 江苏大学 | Preparation method of nickel-coated carbon nanotube efficient hydrogen evolution electrocatalyst |
| CN109714941B (en) * | 2018-11-22 | 2021-02-09 | 谢春艳 | Single-walled carbon nanotube embedded magnetic metal carbon onion nanocomposite and application and preparation method thereof |
| CN110314690B (en) * | 2019-07-16 | 2022-04-19 | 广州大学 | Bimetallic sulfide Ni with heterogeneous interface coupling3S2/FeS composite material and preparation method and application thereof |
| CN111558390B (en) * | 2020-05-14 | 2021-07-06 | 郑州大学 | Preparation method and application of efficient hydrogen evolution catalyst Ir @ NBD-C |
| CN115011228A (en) * | 2022-06-09 | 2022-09-06 | 惠尔明（福建）化学工业股份有限公司 | Waterborne polyurethane coating and preparation method thereof |
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