CN1962431A - Cathode gas film microarc discharging method for preparing carbon nanometer material in solution - Google Patents
Cathode gas film microarc discharging method for preparing carbon nanometer material in solution Download PDFInfo
- Publication number
- CN1962431A CN1962431A CN 200610137895 CN200610137895A CN1962431A CN 1962431 A CN1962431 A CN 1962431A CN 200610137895 CN200610137895 CN 200610137895 CN 200610137895 A CN200610137895 A CN 200610137895A CN 1962431 A CN1962431 A CN 1962431A
- Authority
- CN
- China
- Prior art keywords
- carbon
- cathode
- negative electrode
- solution
- micro
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a carbon nanometer material preparing method through micro-arc discharging of cathode gas film in the solution, which comprises the following steps: adopting acid, alkaline and salt solution as basic electrolyte; applying DC through area rate of cathode and anode; discharging gas film arc on the cathode; adopting high-purity graphite as cathode and carbon source or adopting high purity graphite with doped catalyst as cathode, carbon source and catalyst; or Fe or Co or Ni or their alloy as cathode; adding soluble organics in the basic electrolyte as carbon source; obtaining ocimene, carbon nanometer ball, carbon nanometer flower, carbon nanometer fiber and carbon nanometer pipe; forming diamond film on the cathode surface.
Description
Technical field
The present invention relates to the preparation of carbon nanomaterial, particularly the plasma electric solution prepares carbon nanomaterial.
Background technology
The technology of preparing of carbon nanomaterial related to the present invention is an arc process.Early stage arc process employing closely discharge by Graphite Electrodes in rare gas element prepares carbon nanomaterial, adopts the arc process in hydrogen to prepare carbon nanomaterial afterwards.Nearest many pieces of articles have been reported and produced the method that electric arc prepares carbon nanomaterial in liquid phase environments.For example: A simple method for the continuous production of carbon nanotubes.Chem.Phys.Lett., 319,2000,457 have reported that electric arc prepares carbon nanotube in liquid phase.The liquid phase environment that these institutes adopt comprises liquid nitrogen, deionized water, NaCl, NiSO
4, CoSO
4, FeSO
4, H
3VO
4Deng the aqueous solution, reach the purpose of preparation carbon nanomaterial by the direct discharge of Graphite Electrodes in liquid phase.The relative gaseous phase arc method of this liquid phase arc process has lot of advantages, for example no longer needs vacuum unit, reactant gases and refrigerating unit etc.Yet above-mentioned arc process and liquid phase arc process all are that the direct discharge by two Graphite Electrodess realizes the spacing that electrode must be maintained fixed.Because anode can consume gradually in discharge process, in order to keep the continuity of electric arc, must adopt accurate gearshift to make electrode remain at suitable discharge spacing.In addition, these arc processes need the power supply of the above big electric current of 50A, and energy consumption is bigger.
Summary of the invention
The present invention proposes the method that micro discharge of cathodic gaseous envelope in a kind of aqueous solution prepares carbon nanomaterial, by control cathode and anode area ratio, the air film micro-arc discharge is occurred between negative electrode and the solution, provide carbon source and catalyzer by cathode material or solution, micro discharge of cathodic gaseous envelope obtains carbon fullerene, Nano carbon balls, carbon nanometer flower, carbon nanotube, carbon nanofiber and diamond like carbon film.Not only energy consumption is little to adopt present method, and control is simple.
Specific operation process of the present invention is as follows:
1, with concentration is HCl or the H of 0.01～2mol/L
2SO
4, or H
3PO
4, or the aqueous solution of KOH or NaOH or LiOH or KCl or NaCl or LiCl be basic electrolytic solution, set up electrolyzer.These aqueous solution cathode surface when electrolysis produces hydrogen but does not form other product.
2, the area with negative electrode is controlled at 10～100mm
2In the scope, anode adopts insoluble anode, and cathode and anode area ratio is less than 1.7, and the spacing of cathode and anode is controlled in 10～100mm scope, applies the volts DS of 50～200V between cathode and anode, and negative electrode generates hydrogen membrane generation micro-arc discharge.
3, under above-mentioned 1 and 2 condition, adopt high purity graphite as negative electrode, negative electrode generation air film micro-arc discharge forms black precipitate in solution, precipitation is filtered the back oven dry, obtains carbon nanometer products such as carbon nano powder, carbon nanometer flower and carbon nanofiber.
4, under above-mentioned 1 and 2 condition, employing doping mass percent is 1～10% Fe or Co or Ni or Y, or the high purity graphite of their oxide compound or their mixture is as negative electrode, negative electrode generation air film micro-arc discharge, in solution, form black precipitate, precipitation is filtered the back oven dry, obtain carbon nanometer products such as carbon fullerene, carbon nanofiber and carbon nanotube after the purifying treatment.
5, under above-mentioned 1 and 2 condition, be HCl or the H of 0.01～2mol/L in concentration
2SO
4, or H
3PO
4, or the base water solution of KOH or NaOH or LiOH or KCl or NaCl or LiCl in add alcohol or low molecular organic acids or low molecule organic salt or low molecule aldehyde or the low molecular amine that volume percent is 10～60% water soluble solution; Employing has the Fe of katalysis or Co or Ni or their alloy as negative electrode, negative electrode generation air film micro-arc discharge, in solution, form black precipitate, precipitation is filtered the back oven dry, obtain carbon nanometer products such as carbon fullerene, carbon nanofiber and carbon nanotube after the purifying treatment.
6, under above-mentioned 1,2,5 condition, negative electrode adopts metal or alloy, can deposit diamond like carbon film at cathode surface.
Compared with prior art, the present invention has following characteristics:
The carbon nanomaterial particularly generation of carbon nanotube need possess five conditions simultaneously: the plasma body of carbon source, catalyzer, high energy, the atmosphere of protectiveness (rare gas element, H
2Deng) and favorable cooling effect.Traditional liquid phase arc process is owing to be directly discharge between two electrodes, and what electrode surface formed is the mixed gas of water vapour, hydrogen and oxygen, is unfavorable for the formation of carbon nanotube.
Micro discharge of cathodic gaseous envelope method of the present invention adopts the plasma electrochemical discharge, and the physical chemistry effect that is produced has following effect: 1) energetic plasma of micro discharge of cathodic gaseous envelope generation provides enough energy for the evaporation of carbon; 2) cathode surface has formed hydrogen membrane, for the formation of carbon nanomaterial provides good protection environment; 3) cooling effect of the pulse characteristic that had of air film micro-arc discharge provides powerful motivating force for carbon vapor is deposited as carbon nanomaterial; 4) Graphite Electrodes, or the Graphite Electrodes of doped catalyst, or the organism that dissolves in the aqueous solution provides competent carbon source and catalyzer for carbon nanomaterial.Therefore, micro discharge of cathodic gaseous envelope is that unique favourable condition has been created in the generation of carbon nanomaterial.On the other hand, because micro discharge of cathodic gaseous envelope is to discharge between negative electrode and the solution,, need not accurate electrode step-wise displacement device so the counter electrode spacing without limits.In addition, the arc process that the energy consuming ratio of micro discharge of cathodic gaseous envelope method is traditional comprises that the liquid phase arc process all is much smaller.Therefore, the present invention utilizes the cathode effect of plasma electrolysis can prepare multiple carbon nanomaterials such as carbon fullerene, carbon nano powder, carbon nanofiber, carbon nanotube and diamond like carbon film, for the preparation of carbon nanomaterial provides a kind of economy, easy new way.
Description of drawings
Fig. 1 is the pattern of the carbon nano-particle of embodiment 1 acquisition
Fig. 2 is the pattern of the carbon nanometer flower of embodiment 1 acquisition
Fig. 3 is the pattern of the carbon nanofiber of embodiment 2 acquisitions
Fig. 4 is the high-resolution-ration transmission electric-lens photo of the carbon nanofiber of embodiment 2 acquisitions
Fig. 5 is the pattern of the carbon nanotube of embodiment 3 acquisitions
Fig. 6 is the high-resolution-ration transmission electric-lens photo of the carbon nanotube of embodiment 3 acquisitions
Fig. 7 is the Raman spectrum analysis result of the carbon nanotube of embodiment 3 acquisitions
Fig. 8 is the high resolution scanning electromicroscopic photograph of the diamond like carbon film of embodiment 4 acquisitions
Fig. 9 is the Raman spectrum analysis result of the diamond like carbon film of embodiment 4 acquisitions
Embodiment
Implementing basic skills of the present invention is to set up an electrolyzer, and the volume of electrolyzer is greater than 500mL.Too high for fear of heating up, electrolyzer can be placed a cooling trough or cooling tube is installed.Too fast for fear of solution evaporation, can connect the water-cooled return line on the electrolyzer.The cathode and anode vertical parallel is installed in the electrolyzer.Provide carbon source and catalyzer by negative electrode, or provide carbon source by solution.Guarantee that cathode and anode area ratio is less than 1.7; The spacing of cathode and anode is 10～100mm; Apply the volts DS of 50～200V between the cathode and anode, micro discharge of cathodic gaseous envelope takes place tens of minutes, can in solution, form a large amount of black precipitates, precipitation is filtered the back oven dry, can prepare various carbon nanomaterials after the purifying treatment, comprise carbon fullerene, carbon nano powder, carbon nanometer flower, carbon nanofiber and carbon nanotube, or go out diamond like carbon film at the metal or alloy surface deposition.
Embodiment 1: adopt high purity graphite electrode preparation carbon nanomaterial
HCl or H at 0.25mol/L
2SO
4, or H
3PO
4, or the aqueous solution of KOH or NaOH or LiOH or KCl or NaCl or LiCl in, be that the pure graphite rod of 6mm is an electrode with the diameter, with its surface of PTFE film wrapped, making cathodic surface area is 30mm
2, anode surface area is 60mm
2, 15mm between the cathode and anode applies the direct current of 130V, and cathode micro arc discharge 15min takes place, and obtains the crude product of black precipitate.With after the filtration of crude product at 103 ℃, the HNO of 4M
3Middle backflow 1h, washing is to neutral, at 100 ℃ of air drying 1h.Can obtain carbon nano powder and carbon nanometer flower.Fig. 1 and Fig. 2 are for obtaining the typical pattern of carbon nano powder and carbon nanometer flower.
Embodiment 2: adopt the Graphite Electrodes that contains catalyzer to prepare carbon nanomaterial
HCl or H at 0.25mol/L
2SO
4, or H
3PO
4, or the aqueous solution of KOH or NaOH or LiOH or KCl or NaCl or LiCl in, employing doping mass percent is 5% Fe or Co or Ni or Y, or the high purity graphite of their oxide compound or their mixture is as negative electrode, its diameter is 10mm, with its surface of PTFE film wrapped, reserve 30mm
2Surface-area; It is the pure graphite rod of 6mm that anode adopts diameter, with its surface of PTFE film wrapped, reserves 60mm
2Surface-area, 30mm between the cathode and anode; Apply the direct current of 180V, cathode micro arc takes place depress discharge 15min, obtain the crude product of black precipitate.With after the filtration of crude product at 103 ℃, the HNO of 4M
3Middle backflow 1h, washing is to neutral, at 100 ℃ of air drying 1h.Can obtain carbon nanofiber and carbon nanotube.Fig. 3 and Fig. 4 are the typical photos that obtains carbon nanofiber and carbon nanotube.
Embodiment 3: prepare carbon nanomaterial in containing aqueous organic
Adopt platinum as anode, nickel is negative electrode, keeping negative electrode is 1.0 with the annode area ratio, two electrodes are vertically placed contain the NaCl aqueous solution that volume percent is the 0.25mol/L of 50% ethanol or citric acid or Citrate trianion or crotonic aldehyde or diethanolamine, interelectrode distance is fixed as 20mm, under reflux state, on electrode, apply the voltage of 110V, micro discharge of cathodic gaseous envelope takes place, continue 15min, the solution blackening filters out the back at 103 ℃, the HNO of 4mol/L with the black product in the solution
3Middle backflow 1h, filter in sand core funnel with nylon leaching film the cooling back, and wash to neutrality, and 100 ℃ of oven dry 1h can obtain carbon nanotube in air.Fig. 5, Fig. 6 and Fig. 7 are the typical photo of acquisition carbon nanotube and the analytical results of Raman spectrum.
Embodiment 4: prepare diamond like carbon film in containing aqueous organic
Adopt platinum as anode, adopting carbon steel, nickel-base alloy is negative electrode, negative electrode and annode area are than 1.5, two electrodes are vertically placed contain the NaCl aqueous solution that volume percent is the 0.25mol/L of 40% ethanol or citric acid or Citrate trianion or crotonic aldehyde or diethanolamine, interelectrode distance is fixed as 20mm, applies the voltage of 110V under reflux state on electrode, and micro discharge of cathodic gaseous envelope takes place, continue 15min, can obtain diamond like carbon film at cathode surface.Fig. 8 and Fig. 9 are the surface topography of acquisition diamond like carbon film and the analytical results of Raman spectrum.
In the above-described embodiments,, micro discharge of cathodic gaseous envelope is tending towards definite value when reaching the steady state after-current, about 1～2A, and more much smaller than traditional arc process and liquid phase arc process, thereby have the low advantage of power consumption.
Claims (4)
1, micro discharge of cathodic gaseous envelope prepares the method for carbon nanomaterial in a kind of aqueous solution, it is characterized in that: be HCl or the H of 0.01～2mol/L with concentration
2SO
4, or H
3PO
4, or the aqueous solution of KOH or NaOH or LiOH or KCl or NaCl or LiCl be basic electrolytic solution, set up electrolyzer, the area of negative electrode is controlled at 10～100mm
2In the scope, anode adopts insoluble anode, and cathode and anode area ratio is less than 1.7, and the spacing of cathode and anode is controlled in 10～100mm scope, applies the volts DS of 50～200V between cathode and anode, and negative electrode generates hydrogen membrane generation micro-arc discharge.
2, micro discharge of cathodic gaseous envelope prepares the method for carbon nanomaterial in the aqueous solution as claimed in claim 1, it is characterized in that: adopt high purity graphite as negative electrode, negative electrode generation air film micro-arc discharge, in solution, form black precipitate, precipitation is filtered the back oven dry, obtain carbon nanometer products such as carbon nano powder, carbon nanometer flower and carbon nanofiber.
3, micro discharge of cathodic gaseous envelope prepares the method for carbon nanomaterial in the aqueous solution as claimed in claim 1, it is characterized in that: employing doping mass percent is 1～10% Fe or Co or Ni or Y, or the high purity graphite of their oxide compound or their mixture is as negative electrode, negative electrode generation air film micro-arc discharge, in solution, form black precipitate, precipitation is filtered the back oven dry, obtain carbon nanometer products such as carbon fullerene, carbon nanofiber and carbon nanotube after the purifying treatment.
4, micro discharge of cathodic gaseous envelope prepares the method for carbon nanomaterial in the aqueous solution as claimed in claim 1, it is characterized in that: be HCl or the H of 0.01～2mol/L in concentration
2SO
4, or H
3PO
4, or the base water solution of KOH or NaOH or LiOH or KCl or NaCl or LiCl in add alcohol or low molecular organic acids or low molecule organic salt or low molecule aldehyde or the low molecular amine that volume percent is 10～60% water soluble solution, employing has the Fe of katalysis or Co or Ni or their alloy as negative electrode, negative electrode generation air film micro-arc discharge, in solution, form black precipitate, precipitation is filtered the back oven dry, obtain carbon nanometer products such as carbon fullerene, carbon nanofiber and carbon nanotube after the purifying treatment; Adopt metal or alloy as negative electrode, deposit diamond like carbon film at cathode surface.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101378959A CN100415643C (en) | 2006-11-09 | 2006-11-09 | Cathode gas film microarc discharging method for preparing carbon nanometer material in solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101378959A CN100415643C (en) | 2006-11-09 | 2006-11-09 | Cathode gas film microarc discharging method for preparing carbon nanometer material in solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1962431A true CN1962431A (en) | 2007-05-16 |
| CN100415643C CN100415643C (en) | 2008-09-03 |
Family
ID=38081687
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006101378959A Expired - Fee Related CN100415643C (en) | 2006-11-09 | 2006-11-09 | Cathode gas film microarc discharging method for preparing carbon nanometer material in solution |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100415643C (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103981531A (en) * | 2014-06-03 | 2014-08-13 | 哈尔滨工业大学 | Preparation method of fluorescent carbon dots |
| CN104073834A (en) * | 2013-03-26 | 2014-10-01 | 北京师范大学 | Preparation method of nanometer diamond-like powder |
| CN104294343A (en) * | 2013-07-18 | 2015-01-21 | 北京师范大学 | Preparation method of diamond-like composite carburizing layer of steel surface |
| CN104328451A (en) * | 2014-10-14 | 2015-02-04 | 上海应用技术学院 | Carbon material preparation method |
| CN107541746A (en) * | 2017-09-13 | 2018-01-05 | 西北师范大学 | The method that a kind of liquid phase cathode glow discharging plasma of sacrificial anode leaf prepares nano tungsten trioxide |
| CN108486619A (en) * | 2018-05-08 | 2018-09-04 | 江西理工大学 | The preparation method of graphene oxide-cobalt nanocrystal-DLC film |
| CN113106531A (en) * | 2021-04-22 | 2021-07-13 | 厦门大学 | Method for electrochemically etching diamond semiconductor film |
| CN113461010A (en) * | 2021-07-07 | 2021-10-01 | 南京林业大学 | Method for preparing fluorine-free MXene by adopting electrochemical etching method |
| CN113600824A (en) * | 2021-08-25 | 2021-11-05 | 和超高装(中山)科技有限公司 | Preparation method and preparation device of metal niobium nano powder |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000015869A1 (en) * | 1998-09-11 | 2000-03-23 | Commissariat A L'energie Atomique | Part based on aluminium coated with amorphous hard carbon |
| CN1238563C (en) * | 2002-12-23 | 2006-01-25 | 中国科学院长春光学精密机械与物理研究所 | Nanometer carbon net synthetic method |
| CN1789496A (en) * | 2004-12-15 | 2006-06-21 | 广东工业大学 | Electrochemical preparation method of nano ceric oxide |
| GB2422249A (en) * | 2005-01-15 | 2006-07-19 | Robert John Morse | Power substrate |
-
2006
- 2006-11-09 CN CNB2006101378959A patent/CN100415643C/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104073834A (en) * | 2013-03-26 | 2014-10-01 | 北京师范大学 | Preparation method of nanometer diamond-like powder |
| CN104073834B (en) * | 2013-03-26 | 2017-01-18 | 北京师范大学 | Preparation method of nanometer diamond-like powder |
| CN104294343A (en) * | 2013-07-18 | 2015-01-21 | 北京师范大学 | Preparation method of diamond-like composite carburizing layer of steel surface |
| CN103981531A (en) * | 2014-06-03 | 2014-08-13 | 哈尔滨工业大学 | Preparation method of fluorescent carbon dots |
| CN103981531B (en) * | 2014-06-03 | 2016-04-27 | 哈尔滨工业大学 | A kind of preparation method of fluorescent carbon point |
| CN104328451A (en) * | 2014-10-14 | 2015-02-04 | 上海应用技术学院 | Carbon material preparation method |
| CN107541746A (en) * | 2017-09-13 | 2018-01-05 | 西北师范大学 | The method that a kind of liquid phase cathode glow discharging plasma of sacrificial anode leaf prepares nano tungsten trioxide |
| CN108486619A (en) * | 2018-05-08 | 2018-09-04 | 江西理工大学 | The preparation method of graphene oxide-cobalt nanocrystal-DLC film |
| CN113106531A (en) * | 2021-04-22 | 2021-07-13 | 厦门大学 | Method for electrochemically etching diamond semiconductor film |
| CN113106531B (en) * | 2021-04-22 | 2022-04-08 | 厦门大学 | Method for electrochemically etching diamond semiconductor film |
| CN113461010A (en) * | 2021-07-07 | 2021-10-01 | 南京林业大学 | Method for preparing fluorine-free MXene by adopting electrochemical etching method |
| CN113461010B (en) * | 2021-07-07 | 2023-06-09 | 南京林业大学 | Method for preparing fluorine-free MXene by adopting electrochemical etching method |
| CN113600824A (en) * | 2021-08-25 | 2021-11-05 | 和超高装(中山)科技有限公司 | Preparation method and preparation device of metal niobium nano powder |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100415643C (en) | 2008-09-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100415643C (en) | Cathode gas film microarc discharging method for preparing carbon nanometer material in solution | |
| Song et al. | Ni-foam supported Co (OH) F and Co–P nanoarrays for energy-efficient hydrogen production via urea electrolysis | |
| Kandel et al. | Hybridized bimetallic phosphides of Ni–Mo, Co–Mo, and Co–Ni in a single ultrathin-3D-nanosheets for efficient HER and OER in alkaline media | |
| He et al. | Deposition and electrocatalytic properties of platinum nanoparticals on carbon nanotubes for methanol electrooxidation | |
| Gao et al. | 3D flower-like defected MoS2 magnetron-sputtered on candle soot for enhanced hydrogen evolution reaction | |
| Yang et al. | Cathodic electrochemical activation of Co 3 O 4 nanoarrays: a smart strategy to significantly boost the hydrogen evolution activity | |
| Xia et al. | Electrospun zirconia nanofibers for enhancing the electrochemical synthesis of ammonia by artificial nitrogen fixation | |
| Cheng et al. | High-efficiency bifunctional electrocatalyst based on 3D freestanding Cu foam in situ armored CoNi alloy nanosheet arrays for overall water splitting | |
| Ding et al. | Rose-like Cu-doped Ni3S2 nanoflowers decorated with thin NiFe LDH nanosheets for high-efficiency overall water and urea electrolysis | |
| Rodney et al. | Lanthanum doped copper oxide nanoparticles enabled proficient bi-functional electrocatalyst for overall water splitting | |
| CN107833758B (en) | A kind of preparation method and application of Ni-based integrated electrode | |
| Ma et al. | Three-dimensional crystalline-Ni5P4@ amorphous-NiOx core–shell nanosheets as bifunctional electrode for urea electro-oxidation and hydrogen evolution | |
| CN108212194B (en) | Nitrogen-doped carbon-coated nickel composite nano carbon water electrolysis catalyst and preparation method thereof | |
| Li et al. | Controllable preparation of nitrogen-doped graphitized carbon from molecular precursor as non-metal oxygen evolution reaction electrocatalyst | |
| Hu et al. | Self-supported MoO2-MoO3/Ni2P hybrids as a bifunctional electrocatalyst for energy-saving hydrogen generation via urea–water electrolysis | |
| Su et al. | Facile synthesis of CNC–MnO2 hybrid as a supercapacitor electrode | |
| Wang et al. | Regulating the electronic structure of Ni3S2 nanorods by heteroatom vanadium doping for high electrocatalytic performance | |
| Yu et al. | Cathode glow discharge electrolysis synthesis of flower-like β-Ni (OH) 2 microsphere for high-performance supercapacitor | |
| Naveenraj et al. | Nanosized tantala based materials–synthesis and applications | |
| Wu et al. | Hydrogen evolution reaction activity and stability of sintered porous Ni-Cu-Ti-La2O3 cathodes in a wide pH range | |
| Zhang et al. | Engineering inner-porous cobalt phosphide nanowire based on controllable phosphating for efficient hydrogen evolution in both acidic and alkaline conditions | |
| Wang et al. | Homogeneous pseudoamorphous metal phosphide clusters for ultra stable hydrogen generation by water electrolysis at industrial current density | |
| Rodney et al. | Dysprosium doped copper oxide (Cu1-xDyxO) nanoparticles enabled bifunctional electrode for overall water splitting | |
| Liu et al. | Porous coordination polymer-derived ultrasmall CoP encapsulated in nitrogen-doped carbon for efficient hydrogen evolution in both acidic and basic media | |
| CN112941554B (en) | Composite catalytic electrode and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20080903 Termination date: 20111109 |