CN109136982A - By sacrificing the method to electrode synthesizing nano compound material and its application in electrolysis water catalyst - Google Patents
By sacrificing the method to electrode synthesizing nano compound material and its application in electrolysis water catalyst Download PDFInfo
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Abstract
The invention discloses by sacrificing the method to electrode synthesizing nano compound material and its application in electrolysis water catalyst: carbon nanometer being added dropwise in glass-carbon electrode, carbon nano tube modified glass-carbon electrode is obtained；Precursor A is added in deionized water, adjusting pH is 0~13, obtains electroplate liquid；Carbon nano tube modified glass-carbon electrode is placed in electroplate liquid and implements plating.Precursor B is added in sulfuric acid solution, obtains complex solution, the glass-carbon electrode after being then electroplated is placed in complex solution, selection is to electrode, saturated calomel electrode is reference electrode, obtains the glass-carbon electrode of nanocomposite modification, and composite material is obtained final products from glassy carbon electrode surface removing；The method of the present invention is easy to operate, mild condition, has unique novelty, and composite material obtained produces hydrogen in electro-catalysis, and oxygen is analysed in electro-catalysis, and electrocatalytic oxidation reduction and energy conversion aspect have very big advantage, can be applied to fuel cell and new energy conversion art.
Description
Technical field
The invention belongs to nanocomposite research field and electro-catalysis fields, in particular to a kind of pass through to sacrifice to electrode
The method of synthesizing nano compound material and its application in electrolysis water catalyst.
Background technique
With the development of science and technology, modern society increasingly increases severely to the demand of the energy, hydrogen is received as clean energy resource
The common concern of people.So far, the source of hydrogen depends on fossil energy, such as the steam reformation of natural gas.This
Not only efficiency is very low, at high price for one process, but also the gaseous contaminations atmosphere such as be inevitably generated carbon dioxide.Many institute's weeks
Know, water is reserves substance extremely abundant in nature, therefore in scientific research field, and electrolysis water liberation of hydrogen is always treated as obtaining hydrogen
One highly effective approach of gas.
However, the hydrogen that electrolysis water method prepares only about accounts for the 4% of hydrogen total output, this explanation is now industrial
The main source of hydrogen is also to rely on non-renewable resources.If with the secondary energy sources of these non-renewable energy resources being converted to
Hydrogen does not change the essence for the energy crisis that we face inherently.Hydrogen and water-gas are prepared methane steam reforming
Greenhouse gases equally can be also generated during preparing hydrogen, still endanger our living environment.So developing electrolysis water
The method of hydrogen manufacturing is an ideal approach to obtain hydrogen, because we can use wind power generation, hydroelectric generation, sunlight
Some renewable energy such as power generation provide required electric energy for the process of electrolysis water to prepare hydrogen, and this method can also allow this
A little renewable energy store energy in the form of hydrogen.To sum up, electro-catalysis water-splitting hydrogen manufacturing by the energy can
The important role that sustainable utilization plays.
Although water electrolysis hydrogen production is a good approach to obtain the reproducible new energy of cleaning that we want, but still
There are some technical problems that us is needed to solve.For example the electric energy consumed during electro-catalysis water-splitting is excessively high, the storage of hydrogen
Deposit etc..The electric energy consumed during electrolysis water is excessively high be primarily due to need when electro-catalysis water decomposition it is higher excessively electric
Gesture come promote reaction progress.Present putative ideal electrolysis water catalyst is the platinum based catalyst of noble metal, but due to
These noble metals are expensive to be applied on a large scale so limiting it.In recent years, study it is some it is cheap, to environment without dirt
The base metal of dye becomes the hot spot of research to substitute platinum-base material, still, since the performance of non-precious metal catalyst is universal
Not high, stability is poor, so, practical application effect is not strong.
Therefore, it is necessary to this further improvement.
Summary of the invention
The purpose of the invention is to overcome shortcoming and defect of the existing technology, and provide a kind of by sacrificing to electricity
The application of the method for pole synthesizing nano compound material and the nanocomposite in electrolysis water catalyst.
As the first aspect of the invention, technical solution be the following steps are included:
(1) prepare carbon nano tube modified glass-carbon electrode: carbon nanotube be added in solvent, in 16~40KHz ultrasound 1~
5h forms suspension, which is added dropwise in glassy carbon electrode surface, is dried, to form uniform carbon in glassy carbon electrode surface
Nanotube thin layer obtains carbon nano tube modified glass-carbon electrode；
(2) it prepares electroplate liquid: precursor A being added in deionized water, be 0~13 with ammonium hydroxide and salt acid for adjusting pH, obtain
Electroplate liquid；The precursor A is soluble non-noble metal compound, and the precursor A is final concentration of in electroplate liquid
0.001-10mol/L, non-noble metal j element is tungsten, molybdenum or cobalt in the solubility non-noble metal compound；
(3) base metal carbon nano tube compound material is prepared: the carbon nano tube modified glass-carbon electrode that step (1) is obtained
It is placed in the electroplate liquid that step (2) obtains, is+2~-2V in CV current potential, operation temperature implements electricity under conditions of being 18~35 DEG C
Plating, plating circle number are 1-100 circle, and the non-noble metal compound in electroplate liquid will be deposited in carbon nano tube modified glass-carbon electrode
Surface obtains base metal and the composite modified glass-carbon electrode of carbon nanotube, then that the base metal and carbon nanotube is compound
The glass-carbon electrode of modification is cleaned and dried；
(4) it prepares complex solution: precursor B being added in sulfuric acid solution, obtains complex solution；The precursor B is energy
The compound of complexation of metal ions, wherein the concentration of sulfuric acid solution is 0.001-3mol/L；
(5) sacrifice to electrode synthesizing nano compound material: by base metal that step (3) obtains and carbon nanotube is compound repairs
The glass-carbon electrode of decorations is placed in the complex solution of step (4), selects one or more gold in Pt, Pd, Rh, Ir, Ru, W, Ni, Mo
The silk material for belonging to combined is, using saturated calomel electrode as reference electrode, to construct three-electrode system to electrode, by sacrificing to electrode,
The glass-carbon electrode for being covered with nanocomposite is obtained with electro-plating method, which is expressed as M1-M2- CNTs, wherein
M1=MoSx、CoP、WS2One or more combinations, M2The one or more combinations of=Pt, Pd, Rh, Ir, Ru, W, Ni or Mo, by this
Glass-carbon electrode wash with water it is dry after, composite material scraped from glassy carbon electrode surface with blade obtain it is final nano combined
Material product.
Further setting is the mixing that the solvent in the step (1) is ethyl alcohol, water or ethanol/water volume ratio 1:1~5
Liquid；The volumetric usage of the solvent is calculated as 0.1~2mL/mg with the quality of carbon nanotube.
Further setting is that the glass-carbon electrode before glassy carbon electrode surface is added dropwise in suspension described in the step (1)
Also pre-processed, the preprocess method glass-carbon electrode is successively polished, is washed and in 16~32KHz ultrasound 10~
60s。
Further setting is the precursor A in the step (2) in ammonium thiomolybdate, thio ammonium tungstate, phosphatization cobalt
One or more combinations.
Further setting is the step (2) when preparing electroplate liquid, described in deionized water in addition to precursor A is added
Except, be additionally added the presoma C as buffer substance, and the presoma C in electroplate liquid final concentration of 0.001~
10mmol/L, the presoma C are sodium perchlorate.
It is glycine that further setting, which is precursor B in the step (4), one or more groups in EDTA or sodium chloride
It closes.
Further setting be electroplating parameter described in step (5) are as follows: scanning current potential be 0~-1.8V, scanning speed 1
~500mV/s, operation temperature sweep different circle numbers under conditions of being 18~35 DEG C, scanning circle number is 1~30000cyc；Or electricity
Position is to be electroplated with i-t method, electroplating time is 0.01-50h under conditions of operation temperature is 18~35 DEG C within the scope of -2~2V.
The present invention also provides nanocomposites prepared by a kind of method as mentioned, it is characterised in that: the nanometer is multiple
Condensation material is expressed as M1-M2- CNTs, wherein M1=MoSx、CoP、WS2One or more combinations, M2=Pt, Pd, Rh, Ir, Ru,
W, the one or more combinations of Ni or Mo
The present invention also provides a kind of nanocomposites as mentioned to be applied in electrolysis water reaction as electrolytic catalyst.
In step (1), the carbon nanotube is in single wall, multi wall, array or the carbon nanotube of hetero atom (such as N, S) doping
One or more kinds of arbitrary proportions mixture.In step (1), it is generally the case that the suspension is in the glass carbon electricity
The dripping quantity of pole surface is 50~200 μ L/cm2。
The present invention synthesizes the catalyst of some better performances in three-electrode system with sacrifice to the method for electrode, this to urge
Agent loads the noble metal of some low contents or the cheap metal of better performances using non-precious metal catalyst as substrate, above
Catalyst, has lower overpotential, good catalytic performance and stability, and save at the advantages of combining it both
Cost has stronger practical application value.
Sacrifice of the present invention is controllable to the pore size of composite material made from electrode method (by scanning circle number or i-t
The regulation of electroplating time is realized), and partial size is smaller, active site is more.Obtained composite material can be applied to electro-catalysis
Evolving hydrogen reaction.
The beneficial effects of the present invention are:
(1) substrate selected by is that have in the CNTs (single wall, multi wall, array or Heteroatom doping etc.) of preferable electric conductivity
One or more；
(2) the composite material pore size prepared is controllable, and partial size is from 10nm to 200nm；
(3) the composite active position prepared is more, stable structure；
(4) composite material interface prepared combines very well, is advantageously implemented between the high efficiency of transmission and material of electronics
Synergistic effect preferably plays activity.
In summary, on the one hand, a kind of sacrifice to electrode method provided by the invention prepares nanocomposite, this method behaviour
Make simply, not to be related to high temperature and pressure, can be completed at room temperature, there is unique novelty；On the other hand, pass through suitable condition
Control, composite material obtained have very big advantage in terms of electrocatalytic hydrogen evolution and energy conversion, react in electrocatalytic hydrogen evolution
In, composite material obtained is in 10mA/cm2Under, there is lower overpotential, and the composite material stability is stronger, in electricity
It is catalyzed oxygen to be precipitated, electrocatalytic oxidation reduction etc. also has preferable performance, turns to improve it in fuel cell and photoelectricity
Application value in changing.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention, for those of ordinary skill in the art, without any creative labor, according to
These attached drawings obtain other attached drawings and still fall within scope of the invention.
Fig. 1 is scanning electron microscope diagram piece, the transmission electron microscopy of palladium molybdenum composite material made from the embodiment of the present invention 1
Mirror picture；
Fig. 2 is the linear volt-ampere curve figure of palladium molybdenum composite material made from the embodiment of the present invention 1, Tafel slope figure；
The linear volt-ampere curve figure for the composite material that Fig. 3, which is the present invention, to be synthesized when with different metal silk being to electrode.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, the present invention is made into one below in conjunction with attached drawing
Step ground detailed description.
Embodiment 1: palladium/molybdenum sulfide/carbon nano tube compound material (Pd/MoS is preparedx/CNTs)
(1) pretreatment of electrode: glass-carbon electrode (PINE USA, rotating disk electrode (r.d.e), diameter 5mm) is taken, is successively thrown
Light, washing, the pretreatment of 20KHz ultrasound 60s；
(2) it prepares carbon nano tube modified glass-carbon electrode: a certain amount of array carbon nano tube is added to ethyl alcohol and water volume
In mixed liquor than 1:4, suspension is formed in 40KHz ultrasound 2h, which is added dropwise in through the pretreated glass carbon of step (1)
Electrode surface, naturally dry form uniform carbon nanotube thin layer, obtain carbon nano tube modified glass-carbon electrode；
(3) it prepares electroplate liquid: ammonium thiomolybdate, sodium perchlorate being added in a certain amount of deionized water, with ammonium hydroxide and salt
Acid for adjusting pH is 0~13, obtains electroplate liquid 0.001-10mol/L；
(4) molybdenum sulfide and the compound material of carbon nanotube are prepared: the carbon nano tube modified glass carbon electricity that step (2) is obtained
Pole is placed in the electroplate liquid that step (3) obtains, and is+1~-1V in CV current potential, operation temperature is implemented under conditions of being 18~35 DEG C
Plating, plating time are 1-100 circle, molybdenum sulfide/carbon nano tube compound material glass-carbon electrode are obtained, by the glass-carbon electrode water
After cleaning and spontaneously drying at normal temperature.
(5) it prepares complex solution: precursor B being added in sulfuric acid solution, obtains complex solution；The precursor B is one
The compound (such as glycine, EDTA, sodium chloride etc.) of energy complexation of metal ions a bit, wherein the concentration of sulfuric acid solution is 0.001-
2mol/L。
(1) prepare palladium molybdenum sulfide and the compound material of carbon nanotube: molybdenum sulfide/carbon nanotube that step (4) is obtained is multiple
The glass-carbon electrode of condensation material is placed in the complex solution of step (5), with Pd for electrode, saturated calomel electrode is reference electricity
Pole is 0~-1.8V in scanning current potential, and scanning speed is 1~500mV/s, and operation temperature sweeps difference under conditions of being 18~35 DEG C
Circle number, scanning circle number be 1~30000cyc, obtain being covered with palladium molybdenum sulfide/carbon nano tube compound material glass-carbon electrode, by this
After glass-carbon electrode is washed with water and spontaneously dried at normal temperature, without scraping composite material from electrode surface, electricity is directly carried out
Test chemical.
(7) electro-chemical test: three-electrode system (step (6) preparation be covered with palladium molybdenum sulfide and carbon nanotube it is compound
Material (Pd/MoSx/ CNTs) electrode as working electrode, saturated calomel electrode as reference electrode, graphite electrode as pair
Electrode) in, measure Pd/MoSxThe linear sweep voltammetry curve of/CNTs.The sulfuric acid that test electrolyte solution used is 0.5M is molten
Liquid.Fig. 2 can be seen that in contrast to pure nano-carbon tube and some materials, find composite material in 10mA/cm2Under, have lower
Overpotential, it can be seen that Pd/MoS made from this embodiment examplexHydrogen, which is precipitated, in/CNTs has excellent catalytic activity.
By palladium molybdenum sulfide obtained and the compound material (Pd/MoS of carbon nanotubex/ CNTs) from electrode surface scrape progress
Test, Fig. 1 is the scanning and transmission electron microscopy picture of the composite material, it can be found that the material covered in carbon nanotube
Relatively uniform, particle is smaller, and active site is more；
Embodiment 2: rhodium/molybdenum sulfide/carbon nano tube compound material (Rh/MoS is preparedx/CNTs)
(1) pretreatment of electrode: glass-carbon electrode (PINE USA, rotating disk electrode (r.d.e), diameter 5mm) is taken, is successively thrown
Light, washing, the pretreatment of 20KHz ultrasound 60s；
(2) it prepares carbon nano tube modified glass-carbon electrode: a certain amount of array carbon nano tube is added to ethyl alcohol and water volume
In mixed liquor than 1:4, suspension is formed in 40KHz ultrasound 2h, which is added dropwise in through the pretreated glass carbon of step (1)
Electrode surface, naturally dry form uniform carbon nanotube thin layer, obtain carbon nano tube modified glass-carbon electrode；
(3) it prepares electroplate liquid: ammonium thiomolybdate, sodium perchlorate being added in a certain amount of deionized water, with ammonium hydroxide and salt
Acid for adjusting pH is 0~13, obtains electroplate liquid 0.001-10mol/L；
(4) molybdenum sulfide and the compound material of carbon nanotube are prepared: the carbon nano tube modified glass carbon electricity that step (2) is obtained
Pole is placed in the electroplate liquid that step (3) obtains, and is+1~-1V in CV current potential, operation temperature is implemented under conditions of being 18~35 DEG C
Plating, plating time are 1-100 circle, molybdenum sulfide/carbon nano tube compound material glass-carbon electrode are obtained, by the glass-carbon electrode water
After cleaning and spontaneously drying at normal temperature.
(5) it prepares complex solution: precursor B being added in sulfuric acid solution, obtains complex solution；The precursor B is one
The compound of energy complexation of metal ions a bit, wherein the concentration of sulfuric acid solution is 0.001-2mol/L.
(6) prepare rhodium molybdenum sulfide and the compound material of carbon nanotube: molybdenum sulfide/carbon nanotube that step (4) is obtained is multiple
The glass-carbon electrode of condensation material is placed in the complex solution of step (5), with Rh for electrode, saturated calomel electrode is reference electricity
Pole is to be electroplated with i-t method, electroplating time is under conditions of operation temperature is 18~35 DEG C within the scope of -2~2V in current potential
0.01-50h obtains being covered with rhodium molybdenum sulfide/carbon nano tube compound material glass-carbon electrode, by the glass-carbon electrode wash with water and
After spontaneously drying under room temperature, without scraping composite material from electrode surface, electro-chemical test is directly carried out.
(7) electro-chemical test: three-electrode system (step (6) preparation be covered with rhodium molybdenum sulfide and carbon nanotube it is compound
Material (Rh/MoSx/ CNTs) electrode as working electrode, saturated calomel electrode as reference electrode, graphite electrode as pair
Electrode) in, measure Rh/MoSxThe linear sweep voltammetry curve of/CNTs.The sulfuric acid that test electrolyte solution used is 0.5M is molten
Liquid.
Embodiment 3: palladium/tungsten sulfide/carbon nano tube compound material (Pd/WS is prepared2/CNTs)
(1) pretreatment of electrode: glass-carbon electrode (PINE USA, rotating disk electrode (r.d.e), diameter 5mm) is taken, is successively thrown
Light, washing, the pretreatment of 20KHz ultrasound 60s；
(2) it prepares carbon nano tube modified glass-carbon electrode: a certain amount of array carbon nano tube is added to ethyl alcohol and water volume
In mixed liquor than 1:4, suspension is formed in 40KHz ultrasound 2h, which is added dropwise in through the pretreated glass carbon of step (1)
Electrode surface, naturally dry form uniform carbon nanotube thin layer, obtain carbon nano tube modified glass-carbon electrode；
(3) it prepares electroplate liquid: thio ammonium tungstate, sodium perchlorate being added in a certain amount of deionized water, with ammonium hydroxide and salt
Acid for adjusting pH is 0~13, obtains electroplate liquid 0.001-10mol/L；
(4) tungsten sulfide and the compound material of carbon nanotube are prepared: the carbon nano tube modified glass carbon electricity that step (2) is obtained
Pole is placed in the electroplate liquid that step (3) obtains, and is+1~-1V in CV current potential, operation temperature is implemented under conditions of being 18~35 DEG C
Plating, plating time are 1-100 circle, tungsten sulfide/carbon nano tube compound material glass-carbon electrode are obtained, by the glass-carbon electrode water
After cleaning and spontaneously drying at normal temperature.
(5) it prepares complex solution: precursor B being added in sulfuric acid solution, obtains complex solution；The precursor B is one
The compound (such as glycine, EDTA, sodium chloride etc.) of energy complexation of metal ions a bit, wherein the concentration of sulfuric acid solution is 0.001-
2mol/L。
(6) prepare palladium tungsten sulfide and the compound material of carbon nanotube: tungsten sulfide/carbon nanotube that step (4) is obtained is multiple
The glass-carbon electrode of condensation material is placed in the complex solution of step (5), with Pd for electrode, saturated calomel electrode is reference electricity
Pole is 0~-1.8V in scanning current potential, and scanning speed is 1~500mV/s, and operation temperature sweeps difference under conditions of being 18~35 DEG C
Circle number, scanning circle number be 1~30000cyc, obtain being covered with palladium tungsten sulfide/carbon nano tube compound material glass-carbon electrode, by this
After glass-carbon electrode is washed with water and spontaneously dried at normal temperature, without scraping composite material from electrode surface, electricity is directly carried out
Test chemical.
(7) electro-chemical test: three-electrode system (step (6) preparation be covered with palladium tungsten sulfide and carbon nanotube it is compound
Material (Pd/WS2/ CNTs) electrode as working electrode, saturated calomel electrode is used as reference electrode, graphite electrode to electricity
Pole) in, measure Pd/WS2The linear sweep voltammetry curve of/CNTs.The sulfuric acid solution that test electrolyte solution used is 0.5M.
Embodiment 4: palladium/phosphatization cobalt/carbon nano tube compound material (Pd/CoP is preparedx/CNTs)
(1) pretreatment of electrode: glass-carbon electrode (PINE USA, rotating disk electrode (r.d.e), diameter 5mm) is taken, is successively thrown
Light, washing, the pretreatment of 20KHz ultrasound 60s；
(2) it prepares carbon nano tube modified glass-carbon electrode: a certain amount of array carbon nano tube is added to ethyl alcohol and water volume
In mixed liquor than 1:4, suspension is formed in 40KHz ultrasound 2h, which is added dropwise in through the pretreated glass carbon of step (1)
Electrode surface, naturally dry form uniform carbon nanotube thin layer, obtain carbon nano tube modified glass-carbon electrode；
(3) it prepares electroplate liquid: cobaltous sulfate, sodium hypophosphite being added in a certain amount of deionized water, be 0 with boron acid for adjusting pH
~13, obtain electroplate liquid 0.001-10mol/L；
(4) preparation phosphatization cobalt and the compound material of carbon nanotube: the carbon nano tube modified glass carbon electricity that step (2) is obtained
Pole is placed in the electroplate liquid that step (3) obtains, and is+1.5~-1V in CV current potential, operation temperature is real under conditions of being 18~35 DEG C
Plating is applied, plating time is 1-100 circle, obtains phosphatization cobalt/carbon nano tube compound material glass-carbon electrode, which is used
After water is cleaned and is spontaneously dried at normal temperature.
(5) it prepares complex solution: precursor B being added in sulfuric acid solution, obtains complex solution；The precursor B is one
The compound (such as glycine, EDTA, sodium chloride etc.) of energy complexation of metal ions a bit, wherein the concentration of sulfuric acid solution is 0.001-
2mol/L。
(6) prepare palladium phosphatization cobalt and the compound material of carbon nanotube: phosphatization cobalt/carbon nanotube that step (4) is obtained is multiple
The glass-carbon electrode of condensation material is placed in the complex solution of step (5), with Pd for electrode, saturated calomel electrode is reference electricity
Pole is 0~-1.8V in scanning current potential, and scanning speed is 1~500mV/s, and operation temperature sweeps difference under conditions of being 18~35 DEG C
Circle number, scanning circle number be 1~30000cyc, obtain being covered with palladium phosphatization cobalt/carbon nano tube compound material glass-carbon electrode, by this
After glass-carbon electrode is washed with water and spontaneously dried at normal temperature, without scraping composite material from electrode surface, electricity is directly carried out
Test chemical.
(7) electro-chemical test: three-electrode system (step (6) preparation be covered with palladium phosphatization cobalt and carbon nanotube it is compound
Material (Pd/CoPx/ CNTs) electrode as working electrode, saturated calomel electrode as reference electrode, graphite electrode as pair
Electrode) in, measure Pd/CoPxThe linear sweep voltammetry curve of/CNTs.The sulfuric acid that test electrolyte solution used is 0.5M is molten
Liquid.
The above disclosure is only the preferred embodiments of the present invention, cannot limit the right model of the present invention with this certainly
It encloses, therefore equivalent changes made in accordance with the claims of the present invention, is still within the scope of the present invention.
Claims (9)
1. a kind of method by sacrificing to electrode synthesizing nano compound material, it is characterised in that the following steps are included:
(1) it prepares carbon nano tube modified glass-carbon electrode: carbon nanotube is added in solvent, in 16~40KHz ultrasound 1~5h shape
At suspension, which is added dropwise in glassy carbon electrode surface, is dried, to form uniform carbon nanometer in glassy carbon electrode surface
Pipe thin layer obtains carbon nano tube modified glass-carbon electrode；
(2) it prepares electroplate liquid: precursor A being added in deionized water, be 0~13 with ammonium hydroxide and salt acid for adjusting pH, be electroplated
Liquid；The precursor A is soluble non-noble metal compound, final concentration of 0.001- of the precursor A in electroplate liquid
10mol/L, non-noble metal j element is tungsten, molybdenum or cobalt in the solubility non-noble metal compound；
(3) it prepares base metal carbon nano tube compound material: the carbon nano tube modified glass-carbon electrode that step (1) obtains is placed in
It is+2~-2V in CV current potential, operation temperature implements plating, electricity under conditions of being 18~35 DEG C in the electroplate liquid that step (2) obtains
Plating circle number is 1-100 circle, and the non-noble metal compound in electroplate liquid will be deposited on carbon nano tube modified glassy carbon electrode surface, obtain
The glass-carbon electrode composite modified to base metal and carbon nanotube, the then glass that the base metal and carbon nanotube is composite modified
Carbon electrode is cleaned and dried；
(4) it prepares complex solution: precursor B being added in sulfuric acid solution, obtains complex solution；The precursor B is that can be complexed
The compound of metal ion, wherein the concentration of sulfuric acid solution is 0.001-3mol/L；
(5) sacrifice to electrode synthesizing nano compound material: the base metal and carbon nanotube that step (3) is obtained are composite modified
Glass-carbon electrode is placed in the complex solution of step (4), selects one or more metal groups in Pt, Pd, Rh, Ir, Ru, W, Ni, Mo
The silk material of conjunction is using saturated calomel electrode as reference electrode, three-electrode system to be constructed, by sacrificing to electrode, with electricity to electrode
Electroplating method obtains the glass-carbon electrode for being covered with nanocomposite, which is expressed as M1-M2- CNTs, wherein M1=
MoSx、CoP、WS2One or more combinations, M2The one or more combinations of=Pt, Pd, Rh, Ir, Ru, W, Ni or Mo, by the glass carbon
After electrode water is cleaned and dried, composite material is scraped from glassy carbon electrode surface with blade and obtains final nanocomposite
Product.
2. a kind of method by sacrificing to electrode synthesizing nano compound material according to claim 1, it is characterised in that:
Solvent in the step (1) is the mixed liquor of ethyl alcohol, water or ethanol/water volume ratio 1:1~5；The volumetric usage of the solvent
0.1~2mL/mg is calculated as with the quality of carbon nanotube.
3. a kind of method by sacrificing to electrode synthesizing nano compound material according to claim 1, it is characterised in that:
Suspension described in the step (1) is added dropwise before glassy carbon electrode surface, which is also pre-processed, the pretreatment
Glass-carbon electrode is successively polished, is washed and in 16~32KHz ultrasound, 10~60s by method.
4. a kind of method by sacrificing to electrode synthesizing nano compound material according to claim 1, it is characterised in that:
Precursor A in the step (2) is ammonium thiomolybdate, thio ammonium tungstate, one or more combinations in phosphatization cobalt.
5. a kind of method by sacrificing to electrode synthesizing nano compound material according to claim 1, it is characterised in that:
The step (2) is described in deionized water other than precursor A is added when preparing electroplate liquid, is additionally added as buffering
The presoma C of substance, and the presoma C final concentration of 0.001~10mmol/L in electroplate liquid, the presoma C
For sodium perchlorate.
6. a kind of method by sacrificing to electrode synthesizing nano compound material according to claim 1, it is characterised in that:
Precursor B in the step (4) is glycine, one or more combinations in EDTA or sodium chloride.
7. a kind of method by sacrificing to electrode synthesizing nano compound material according to claim 1, it is characterised in that:
Electroplating parameter described in step (5) are as follows: scanning current potential as 0~-1.8V, scanning speed is 1~500mV/s, and operation temperature is
Different circle numbers is swept under conditions of 18~35 DEG C, scanning circle number is 1~30000cyc；Or current potential is to use within the scope of -2~2V
The plating of i-t method, electroplating time is 0.01-50h under conditions of operation temperature is 18~35 DEG C.
8. nanocomposite prepared by a kind of method as described in one of claim 1-7, it is characterised in that: the nanometer is multiple
Condensation material is expressed as M1-M2- CNTs, wherein M1=MoSx、CoP、WS2One or more combinations, M2=Pt, Pd, Rh, Ir, Ru,
W, the one or more combinations of Ni or Mo.
9. a kind of nanocomposite as described in 8 is applied in electrolysis water reaction as electrolytic catalyst.
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Cited By (4)
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| CN109609973A (en) * | 2018-12-11 | 2019-04-12 | 温州大学 | The preparation method and application of the carbon nano-tube modified load low content palladium composite material of organic sulfur compound |
| CN111334821A (en) * | 2020-02-28 | 2020-06-26 | 江苏大学 | High-efficiency nickel phosphide electrolysis water hydrogen evolution catalytic electrode under neutral condition and preparation method thereof |
| CN111334820A (en) * | 2020-02-24 | 2020-06-26 | 江苏大学 | Low-cost and high-efficiency Ni-P series hydrogen evolution electrode and preparation method thereof |
| CN112501631A (en) * | 2020-10-14 | 2021-03-16 | 温州大学 | Noble metal rhodium hydrogen evolution electrocatalyst and application |
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| CN107937967A (en) * | 2017-10-25 | 2018-04-20 | 温州大学 | The transition metal phosphide carbon nano tube compound material of multi-pore channel and its preparation method based on small molecule regulation and application |
| CN108220996A (en) * | 2017-12-27 | 2018-06-29 | 温州大学 | A kind of molybdenum platinum is composite porous and its preparation method and application |
| CN108273524A (en) * | 2017-12-27 | 2018-07-13 | 温州大学 | A kind of carbon composite and the preparation method and application thereof of chalcogen compound and transition metal modification |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107937967A (en) * | 2017-10-25 | 2018-04-20 | 温州大学 | The transition metal phosphide carbon nano tube compound material of multi-pore channel and its preparation method based on small molecule regulation and application |
| CN108220996A (en) * | 2017-12-27 | 2018-06-29 | 温州大学 | A kind of molybdenum platinum is composite porous and its preparation method and application |
| CN108273524A (en) * | 2017-12-27 | 2018-07-13 | 温州大学 | A kind of carbon composite and the preparation method and application thereof of chalcogen compound and transition metal modification |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109609973A (en) * | 2018-12-11 | 2019-04-12 | 温州大学 | The preparation method and application of the carbon nano-tube modified load low content palladium composite material of organic sulfur compound |
| CN109609973B (en) * | 2018-12-11 | 2020-12-22 | 温州大学 | Preparation method and application of organic sulfide modified carbon nanotube loaded low-content palladium composite material |
| CN111334820A (en) * | 2020-02-24 | 2020-06-26 | 江苏大学 | Low-cost and high-efficiency Ni-P series hydrogen evolution electrode and preparation method thereof |
| CN111334821A (en) * | 2020-02-28 | 2020-06-26 | 江苏大学 | High-efficiency nickel phosphide electrolysis water hydrogen evolution catalytic electrode under neutral condition and preparation method thereof |
| CN112501631A (en) * | 2020-10-14 | 2021-03-16 | 温州大学 | Noble metal rhodium hydrogen evolution electrocatalyst and application |
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