CN109806898A - A kind of nitrogen co-doped carbon material of boron and the preparation method and application thereof - Google Patents
A kind of nitrogen co-doped carbon material of boron and the preparation method and application thereof Download PDFInfo
- Publication number
- CN109806898A CN109806898A CN201910048244.XA CN201910048244A CN109806898A CN 109806898 A CN109806898 A CN 109806898A CN 201910048244 A CN201910048244 A CN 201910048244A CN 109806898 A CN109806898 A CN 109806898A
- Authority
- CN
- China
- Prior art keywords
- carbon material
- boron
- nitrogen
- boron nitride
- doped carbon
- 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
- Catalysts (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention belongs to technical field prepared by catalyst and ammonia, a kind of nitrogen co-doped carbon material of boron and the preparation method and application thereof is disclosed.Method: boron nitride is respectively placed in the different pyroreaction regions of reaction unit from carbon material, and boron nitride is located at the top of air-flow, carbon material is located at the lower section of air-flow；Under the flowing of carrier gas, vapor is delivered to region locating for boron nitride, and boron nitride and vapor carry out pyroreaction, obtains presoma small molecule；Presoma small molecule is delivered to region locating for carbon material with air-flow, and carbon material carries out codope with presoma small molecule and reacts, and obtains the nitrogen co-doped carbon material of boron；The temperature of pyroreaction is 800~1200 DEG C；The temperature of codope reaction is 500~900 DEG C.Method of the invention, simply, at low cost, raw material is cheap and easy to get, environmentally protective.For the nitrogen co-doped carbon material of the boron of preparation when being catalyzed nitrogen ammonia, catalytic efficiency is good.The nitrogen co-doped carbon material of boron is for being catalyzed nitrogen ammonia.
Description
Technical field
The invention belongs to technical field prepared by catalyst and ammonia, in particular to the nitrogen co-doped carbon material of a kind of boron and
Preparation method and application.Application of the nitrogen co-doped carbon material of boron in the preparation of ammonia is used as catalyst, especially nitrogen
The catalyst of ammonia processed is restored, catalysis nitrogen restores ammonia processed.
Background technique
Ammonia is a kind of very important compound and industrial fertilizer.It is multiple that it can be used for manufacturing ammonium hydroxide, nitrogenous fertilizer urea, carbon hinge etc.
Substances, these substances such as Hefei material, nitric acid, hinge salt, soda ash are applied to chemical industry, light industry, chemical fertilizer, pharmacy, synthesis extensively
The fields such as fiber.Furthermore industrial itrogenous organic substance intermediate, sulfa drug, polyurethane, poly- phthalein amine fiber and butyronitrile rubber
Deng also all needing directly using ammonia as raw material.It is continuously increased along with the energy shortage, environmental pollution and the size of population that become increasingly conspicuous
Problem will certainly cause the whole world to be continuously increased ammonia demand, and up to the present the yield of the annual ammonia in the whole world is up to 20
Hundred million tons.Therefore, explore high efficiency, high yield, low energy consumption, with environmental-friendly synthesis ammonia method have become guarantee the whole world can hold
The inevitable requirement of supervention exhibition.
The Haber-Bosch legal system ammonia for having had more than 100 years history is still the main route of industrial production ammonia.The party
Method is mainly to utilize the effect of metallic catalyst, by the hydrogen in the nitrogen and water in air in 400-500 DEG C and the pressure of 130-170 pa
It is chemically reacted under power.The equation of reaction: 3H2+N2=2NH3.The condition of the entire production process of this method is very harsh,
It not only needs metal Ru or Fe etc. as catalyst, but also needs high temperature and pressure.
So far, the research emphasis of ammonia catalyst processed still concentrates on noble metal (Pt, Ru, Au etc.) material, because
Noble metal shows high catalytic activity in reduction ammonia-preparing process.However, noble metal is rare, expensive, significantly limit
Industrialized application.Therefore, rich reserves, cheap non-precious metal catalyst (such as Mo nanometer film, Fe2O3- CNT) and it is non-
Metallic catalyst (such as N adulterates porous carbon, and N adulterates porous carbon MOF, B doped graphene) is furtherd investigate, but makes to be used to close
The yield and its Faraday effect of ammonification are still very limited.Therefore, base metal or nonmetallic catalysis how further to be promoted
Efficiency, system stability and the searching substitutes such as base metal or non-metallic catalyst are a technical problem to be solved urgently
And difficult point.
Summary of the invention
In order to overcome shortcoming and defect existing in the prior art, the purpose of the present invention is to provide a kind of boron is nitrogen co-doped
Carbon material and preparation method thereof.Preparation method of the invention is simple, efficient, low in cost, yield is high, industrialization is expected high.Institute
The nitrogen co-doped carbon material of the boron of acquisition is non-noble metal material, when being catalyzed nitrogen reduction ammonia processed, has preferable catalysis effect
Rate.
Another object of the present invention is to provide the applications of the nitrogen co-doped carbon material of above-mentioned boron.The nitrogen co-doped carbon materials of boron
Expect the application in the preparation in ammonia, is used as the catalyst that catalyst, especially nitrogen restore ammonia processed, catalysis nitrogen reduction system
Ammonia.
To achieve the above object, the present invention adopts the following technical scheme that:
A kind of preparation method of the nitrogen co-doped carbon material of boron, comprising the following steps:
Boron nitride is respectively placed in the different pyroreaction regions of reaction unit from carbon material, and boron nitride is located at air-flow
Top, carbon material is located at the lower section of air-flow；Under the flowing of carrier gas, vapor is delivered to region locating for boron nitride, nitridation
Boron and vapor carry out pyroreaction, obtain presoma small molecule；Presoma small molecule is delivered to locating for carbon material with air-flow
Region, carbon material and presoma small molecule carry out codope and react, and obtains the nitrogen co-doped carbon material of boron.
The temperature of the pyroreaction is 800~1200 DEG C, and the time of pyroreaction is 1~5h；
The temperature of the codope reaction is 500~900 DEG C, and the time of codope reaction is 1~5h, preferably 1~3h.
The heating rate of the pyroreaction is 5-20 DEG C/min；The heating rate of codope reaction is 5-20 DEG C/
min。
The carrier gas is inert gas, such as: argon gas；The flow rate of carrier gas is 50-500mL/min.
The mass ratio of the boron nitride and carbon material is (2~8): 1, preferably (4~8): 1.
The preparation method of the nitrogen co-doped carbon material of boron, specifically includes the following steps:
Boron nitride is respectively placed in the different high temperature reaction zones of reaction unit from carbon material, and boron nitride is close to air inlet
End, carbon material lean near outgassing end；Water is placed on to the inlet end of reaction unit, reaction unit heats up in an inert atmosphere, and water steams
Hair is vapor, and enters the high temperature reaction zone where boron nitride with inert gas, and vapor and boron nitride progress high temperature are anti-
It answers, obtains presoma small molecule；Presoma small molecule enters the high temperature reaction zone where carbon material with air-flow, and small point of presoma
Son carries out codope with carbon material and reacts, and obtains the nitrogen co-doped carbon material of boron.
The mass ratio of the boron nitride and water is 1:(80~100).
The nitrogen content of the nitrogen co-doped carbon material of boron is 4-7%, boron content 3-4.5%.
The reaction unit is double temperature-area tubular furnaces.
The carbon material is the carbon material with oxygen-containing functional group.
Application of the nitrogen co-doped carbon material of boron in the preparation of ammonia is used as catalyst, especially nitrogen and restores ammonia processed
Catalyst, catalysis nitrogen restores ammonia processed.
The present invention passes through the doping of nitrogen, boron, not only can change the electric conductivity of carbon material, can also inhibit reduction ammonia mistake processed
Evolving hydrogen reaction in journey, to further increase the reduction activation and selectivity of catalyst.
Compared with prior art, the invention has the following advantages and beneficial effects:
Method of the invention is efficient, simply, at low cost, raw materials used cheap and easy to get, environmentally protective.Relative to metal catalytic
Material, the present invention greatly reduce catalysis cost.Relative to other non-metallic catalysts, this invention simplifies production procedures.This
The nitrogen co-doped carbon material of boron of preparation is invented when being catalyzed nitrogen ammonia, catalytic efficiency with higher.
Detailed description of the invention
Fig. 1 is the XPS figure of the nitrogen co-doped carbon material of boron of embodiment 6；Figure a is that x-ray photoelectron spectroscopy (XPS) is composed entirely
Figure；Figure b and figure c is respectively the XPS element swarming figure of the nitrogen co-doped carbon material of boron, and figure b corresponds to B 1s, and figure c corresponds to N 1s；
Fig. 2 is the scanning electron microscope (SEM) photograph for the nitrogen co-doped carbon material of boron that embodiment 6 obtains；
Fig. 3 is the nitrogen co-doped carbon material linear sweep voltammetry figure of boron that embodiment 6 obtains.
Specific embodiment
Illustrate technical solution of the present invention combined with specific embodiments below, but the scope of the present invention is not limited thereto.
Reagent, material and the instrument arrived used in embodiment such as not special explanation, be conventional reagent, conventional material and
Conventional instrument, commercially available, related reagent can also be synthesized by conventional synthesis process and be obtained.
Embodiment 1
Boron nitride 0.2g and carbon material 0.1g are respectively placed in the center of the different warm areas of double temperature-area tubular furnaces two；Institute
Stating the distance between boron nitride and carbon material is 15cm；In placement 20mL distilled water (air inlet in one end outside warm area where boron nitride
End), tube furnace is heated up (heating rate of two warm areas is 5 DEG C/min), the distilled water quilt in temperature-rise period, outside warm area
The evaporation of air inlet warm area waste heat, generates a large amount of vapor；It first extracts inner air tube before heating out and is supplemented with argon gas, argon gas conduct
Carrier gas, acts on entire experiment, and argon gas flow velocity is 50mL/min.Argon gas carries warm area where vapor enters boron nitride and carries out instead
It answers, the temperature of warm area where boron nitride is 1200 DEG C, and vapor is reacted with boron nitride, keeps the temperature 1h, obtains presoma small molecule；Before
High temperature reaction zone where body small molecule enters carbon material with air-flow is driven, the temperature of warm area where carbon material is 800 DEG C, boron oxide
Codope is carried out with carbon material with ammonia to react, continues 5h, obtains the nitrogen co-doped carbon material of boron.
Carbon material is graphene oxide in the present embodiment.
The nitrogen co-doped carbon material of boron manufactured in the present embodiment is used to be catalyzed nitrogen and restores ammonia processed, comprising the following steps:
It selects 0.05mol/L sulfuric acid solution for electrolyte, takes 30mL in two Room respectively；Using three-electrode system, Pt electrode
For to electrode, Ag/AgCl is reference electrode, the nitrogen co-doped carbon material of boron (working electrode) is tested at room temperature, is led to before measuring
Enter pure nitrogen gas (99.99%) to cathode chamber 30min, so that electrolyte environment is become nitrogen saturation state, then carry out constant potential survey
Examination.The performance test results of the nitrogen co-doped carbon material of the boron of the present embodiment: faradic efficiency 0.6%, the yield of ammonia are 1.7 μ
g·h-1·mgcat. -1。
Embodiment 2
Boron nitride 0.8g and carbon material 0.1g are respectively placed in the center of the different warm areas of double temperature-area tubular furnaces two；Institute
Stating the distance between boron nitride and carbon material is 15cm；In placement 80mL distilled water (air inlet in one end outside warm area where boron nitride
End), tube furnace is heated up (heating rate of two warm areas is 10 DEG C/min), the distilled water in temperature-rise period, outside warm area
It is evaporated by air inlet warm area waste heat, generates a large amount of vapor；It first extracts inner air tube before heating out and is supplemented with argon gas, argon gas is made
For carrier gas, entire experiment is acted on, argon gas flow velocity is 100mL/min.Argon gas carry vapor enter warm area where boron nitride into
Row reaction, the temperature of warm area where boron nitride are 800 DEG C, and vapor is reacted with boron nitride, keeps the temperature 3h, obtain small point of presoma
Son；Presoma small molecule enters the high temperature reaction zone where carbon material with air-flow, and the temperature of warm area where carbon material is 500
DEG C, boron oxide and ammonia and carbon material carry out codope, keep the temperature 2h, obtain the nitrogen co-doped carbon material of boron.
Carbon material is graphene oxide in the present embodiment.
By the nitrogen co-doped carbon material of boron manufactured in the present embodiment be used to be catalyzed nitrogen restore ammonia processed, specific steps and condition with
Embodiment 1 is identical.The performance test results of the nitrogen co-doped carbon material of the boron of the present embodiment: faradic efficiency 0.5%, the production of ammonia
Rate is 2.6 μ gh-1·mgcat. -1。
Embodiment 3
Boron nitride 0.8g and carbon material 0.1g are respectively placed in the center of the different warm areas of double temperature-area tubular furnaces two；?
80mL distilled water (inlet end) is placed in the outer one end of warm area where boron nitride, and tube furnace is heated up the (heating rate of two warm areas
For 15 DEG C/min), in temperature-rise period, the distilled water outside warm area is evaporated by air inlet warm area waste heat, generates a large amount of vapor；It rises
It first extracts inner air tube before temperature out and is supplemented with argon gas, argon gas acts on entire experiment as carrier gas, and argon gas flow velocity is 200mL/
min.Argon gas carries warm area where vapor enters boron nitride and is reacted, and the temperature of warm area where boron nitride is 1000 DEG C, water
Steam is reacted with boron nitride, keeps the temperature 2h, obtains presoma small molecule；Presoma small molecule enters the high temperature of carbon material with air-flow
Reaction zone, the temperature of warm area where carbon material are 800 DEG C, and boron oxide and ammonia and carbon material carry out codope, keep the temperature 3h, are obtained
The nitrogen co-doped carbon material of boron.
Carbon material is graphene oxide in the present embodiment.
By the nitrogen co-doped carbon material of boron manufactured in the present embodiment be used to be catalyzed nitrogen restore ammonia processed, specific steps and condition with
Embodiment 1 is identical.The performance test results of the nitrogen co-doped carbon material of the boron of the present embodiment: faradic efficiency 1%, the yield of ammonia
For 2.8 μ gh-1·mgcat. -1。
Embodiment 4
Boron nitride 0.8g and carbon material 0.1g are respectively placed in the center of the different warm areas of double temperature-area tubular furnaces two；?
80mL distilled water (inlet end) is placed in the outer one end of warm area where boron nitride, and tube furnace is heated up the (heating rate of two warm areas
For 20 DEG C/min), in temperature-rise period, the distilled water outside warm area is evaporated by air inlet warm area waste heat, generates a large amount of vapor；It rises
It first extracts inner air tube before temperature out and is supplemented with argon gas, argon gas acts on entire experiment as carrier gas, and argon gas flow velocity is 300mL/
min.Argon gas carries warm area where vapor enters boron nitride and is reacted, and the temperature of warm area where boron nitride is 1100 DEG C, water
Steam is reacted with boron nitride, keeps the temperature 2h, obtains presoma small molecule；Presoma small molecule enters the high temperature of carbon material with air-flow
Reaction zone, the temperature of warm area where carbon material are 900 DEG C, and boron oxide and ammonia and carbon material carry out codope, keep the temperature 1h, are obtained
The nitrogen co-doped carbon material of boron.
Carbon material is graphene oxide in the present embodiment.
By the nitrogen co-doped carbon material of boron manufactured in the present embodiment be used to be catalyzed nitrogen restore ammonia processed, specific steps and condition with
Embodiment 1 is identical.The performance test results of the nitrogen co-doped carbon material of the boron of the present embodiment: faradic efficiency 1.2%, the production of ammonia
Rate is 2.5 μ gh-1·mgcat. -1。
Embodiment 5
Boron nitride 0.8g and carbon material 0.1g are respectively placed in the center of the different warm areas of double temperature-area tubular furnaces two；?
80mL distilled water (inlet end) is placed in the outer one end of warm area where boron nitride, and tube furnace is heated up the (heating rate of two warm areas
For 15 DEG C/min), in temperature-rise period, the distilled water outside warm area is evaporated by air inlet warm area waste heat, generates a large amount of vapor；It rises
It first extracts inner air tube before temperature out and is supplemented with argon gas, argon gas acts on entire experiment as carrier gas, and argon gas flow velocity is 400mL/
min.Argon gas carries warm area where vapor enters boron nitride and is reacted, and the temperature of warm area where boron nitride is 1100 DEG C, water
Steam is reacted with boron nitride, keeps the temperature 2h, obtains presoma small molecule；Presoma small molecule enters where carbon material with air-flow
High temperature reaction zone, the temperature of warm area where carbon material are 800 DEG C, and boron oxide and ammonia and carbon material carry out codope, keep the temperature 1h,
Obtain the nitrogen co-doped carbon material of boron.
Carbon material is graphene oxide in the present embodiment.
By the nitrogen co-doped carbon material of boron manufactured in the present embodiment be used to be catalyzed nitrogen restore ammonia processed, specific steps and condition with
Embodiment 1 is identical.The performance test results of the nitrogen co-doped carbon material of the boron of the present embodiment: faradic efficiency 1.5%, the production of ammonia
Rate is 3.1 μ gh-1·mgcat. -1。
Embodiment 6
Boron nitride 0.8g and carbon material 0.1g are respectively placed in the center of the different warm areas of double temperature-area tubular furnaces two；?
80mL distilled water (inlet end) is placed in the outer one end of warm area where boron nitride, and tube furnace is heated up the (heating rate of two warm areas
For 15 DEG C/min), in temperature-rise period, the distilled water outside warm area is evaporated by air inlet warm area waste heat, generates a large amount of vapor；It rises
It first extracts inner air tube before temperature out and is supplemented with argon gas, argon gas acts on entire experiment as carrier gas, and argon gas flow velocity is 500mL/
min.Argon gas carries warm area where vapor enters boron nitride and is reacted, and the temperature of warm area where boron nitride is 1000 DEG C, water
Steam is reacted with boron nitride, keeps the temperature 3h, obtains presoma small molecule；Presoma small molecule enters where carbon material with air-flow
High temperature reaction zone, the temperature of warm area where carbon material are 900 DEG C, and boron oxide and ammonia and carbon material carry out codope, keep the temperature 1h,
Obtain the nitrogen co-doped carbon material of boron.
Carbon material is graphene oxide in the present embodiment.
By the nitrogen co-doped carbon material of boron manufactured in the present embodiment be used to be catalyzed nitrogen restore ammonia processed, specific steps and condition with
Embodiment 1 is identical.
The performance test results of the nitrogen co-doped carbon material of the boron of the present embodiment: faradic efficiency 6.27%, the yield of ammonia
For 38.76 μ gh-1·mgcat. -1。
Fig. 1 is the XPS figure of the nitrogen co-doped carbon material of boron of embodiment 6；Figure a is the full spectrogram of XPS；Scheming b and figure c is respectively boron
The XPS element swarming figure of nitrogen co-doped carbon material；Figure b corresponds to B 1s, and figure c corresponds to N 1s.From figure 1 it appears that B and N member
Element passes through doping reaction, is introduced on the skeleton of carbon material, forms stable C-B and C-N key, so that it is total to improve boron nitrogen
Adulterate the catalytic performance of carbon material.
Fig. 2 is the scanning electron microscope (SEM) photograph for the nitrogen co-doped carbon material of boron that embodiment 6 obtains.
Fig. 3 is the linear sweep voltammetry figure for the nitrogen co-doped carbon material of boron that embodiment 6 obtains.
The catalysis nitrogen ammonia performance of the gained nitrogen co-doped carbon material of boron of the invention is better than most of catalyst, wherein farad
Efficiency is 6.27%, and the yield of ammonia is 38.76 μ gh-1·mgcat. -1。
Carbon material employed in embodiment is using classical Hummer ' s graphene oxide preparation method:
1) 5g graphite powder and 2.5g NaNO are taken3, it is added in the 150mL concentrated sulfuric acid, 15min is stirred in ice-water bath；
2) it is slowly added to 15g KMnO42h is stirred in (temperature is lower than 20 DEG C), continuation in ice-water bath, and reaction system becomes ink
Green；
3) 35 DEG C are warming up to, after reacting 30min, 200mL water is added；
4) it moves into 98 DEG C of oil baths, reacts 90min, reaction system becomes dark yellow；
5) it is diluted to 500mL with 60 DEG C of water, the H of 35mL is added2O2(temperature at this time or 98 DEG C).
6) solution dilute HCl and water washing, is freeze-dried after centrifugation.
Claims (9)
1. a kind of preparation method of the nitrogen co-doped carbon material of boron, it is characterised in that: the following steps are included:
Boron nitride is respectively placed in the different pyroreaction regions of reaction unit from carbon material, and boron nitride is located at the upper of air-flow
Side, carbon material are located at the lower section of air-flow；Under the flowing of carrier gas, vapor is delivered to region locating for boron nitride, boron nitride with
Vapor carries out pyroreaction, obtains presoma small molecule；Presoma small molecule is delivered to area locating for carbon material with air-flow
Domain, carbon material carry out codope with presoma small molecule and react, and obtain the nitrogen co-doped carbon material of boron；The temperature of the pyroreaction
It is 800~1200 DEG C；The temperature of the codope reaction is 500~900 DEG C.
2. the preparation method of the nitrogen co-doped carbon material of boron according to claim 1, it is characterised in that: the carrier gas is indifferent gas
Body；The flow rate of carrier gas is 50-500mL/min；
The mass ratio of the boron nitride and carbon material is (2~8): 1.
3. the preparation method of the nitrogen co-doped carbon material of boron according to claim 2, it is characterised in that:
The mass ratio of the boron nitride and carbon material is (4~8): 1.
4. the preparation method of the nitrogen co-doped carbon material of boron according to claim 1, it is characterised in that: the pyroreaction when
Between be 1~5h；The time of the codope reaction is 1~5h；
The heating rate of the pyroreaction is 5-20 DEG C/min；The heating rate of the codope reaction is 5-20 DEG C/min.
5. the preparation method of the nitrogen co-doped carbon material of boron according to claim 1, it is characterised in that: specifically include following step
It is rapid:
Boron nitride is respectively placed in the different high temperature reaction zones of reaction unit from carbon material, and boron nitride is close to inlet end, carbon
Material leans near outgassing end；Water is placed on to the inlet end of reaction unit, reaction unit heats up in an inert atmosphere, and water evaporation is water
Steam, and enter the high temperature reaction zone where boron nitride with inert gas, vapor and boron nitride carry out pyroreaction, obtain
Presoma small molecule；Presoma small molecule enters the high temperature reaction zone where carbon material, presoma small molecule and carbon with air-flow
Material carries out codope reaction, obtains the nitrogen co-doped carbon material of boron.
6. the preparation method of the nitrogen co-doped carbon material of boron according to claim 5, it is characterised in that: the boron nitride and water
Mass ratio is 1:(80~100)；
The carbon material is the carbon material with oxygen-containing functional group.
7. a kind of nitrogen co-doped carbon material of boron obtained by any one of claim 1~6 preparation method.
8. application of the nitrogen co-doped carbon material of boron in the preparation of ammonia according to claim 7.
9. application according to claim 8, it is characterised in that: the nitrogen co-doped carbon material of boron is used as nitrogen and restores ammonia processed
Catalyst, catalysis nitrogen restores ammonia processed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910048244.XA CN109806898B (en) | 2019-01-18 | 2019-01-18 | Boron-nitrogen co-doped carbon material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910048244.XA CN109806898B (en) | 2019-01-18 | 2019-01-18 | Boron-nitrogen co-doped carbon material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109806898A true CN109806898A (en) | 2019-05-28 |
| CN109806898B CN109806898B (en) | 2021-05-14 |
Family
ID=66603527
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910048244.XA Active CN109806898B (en) | 2019-01-18 | 2019-01-18 | Boron-nitrogen co-doped carbon material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109806898B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110540196A (en) * | 2019-09-17 | 2019-12-06 | 华南理工大学 | boron-nitrogen co-doped porous graphene and preparation method and application thereof |
| CN113292769A (en) * | 2021-06-21 | 2021-08-24 | 青岛睿智森油封有限公司 | Self-lubricating sealing material and preparation method thereof |
| CN115475641A (en) * | 2022-07-27 | 2022-12-16 | 齐鲁工业大学 | Metal atom anchored boron-nitrogen co-doped carbon material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105349114A (en) * | 2015-10-27 | 2016-02-24 | 中国科学院深圳先进技术研究院 | Boron nitride doped composite material and preparation method and application thereof |
| CN106914268A (en) * | 2017-04-12 | 2017-07-04 | 郑州汉东科技有限公司 | A kind of graphene composite nano material and its preparation method and application |
| CN107961793A (en) * | 2017-11-27 | 2018-04-27 | 山西大同大学 | Nickel cobalt oxyhydroxide adulterates the analysis oxygen catalysis material of graphene oxide |
-
2019
- 2019-01-18 CN CN201910048244.XA patent/CN109806898B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105349114A (en) * | 2015-10-27 | 2016-02-24 | 中国科学院深圳先进技术研究院 | Boron nitride doped composite material and preparation method and application thereof |
| CN106914268A (en) * | 2017-04-12 | 2017-07-04 | 郑州汉东科技有限公司 | A kind of graphene composite nano material and its preparation method and application |
| CN107961793A (en) * | 2017-11-27 | 2018-04-27 | 山西大同大学 | Nickel cobalt oxyhydroxide adulterates the analysis oxygen catalysis material of graphene oxide |
Non-Patent Citations (1)
| Title |
|---|
| XIAOMIN YU ET AL: ""Boron-Doped Graphene for Electrocatalytic N2 Reduction"", 《JOULE》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110540196A (en) * | 2019-09-17 | 2019-12-06 | 华南理工大学 | boron-nitrogen co-doped porous graphene and preparation method and application thereof |
| CN113292769A (en) * | 2021-06-21 | 2021-08-24 | 青岛睿智森油封有限公司 | Self-lubricating sealing material and preparation method thereof |
| CN113292769B (en) * | 2021-06-21 | 2022-04-26 | 青岛睿智森油封有限公司 | Self-lubricating sealing material and preparation method thereof |
| CN115475641A (en) * | 2022-07-27 | 2022-12-16 | 齐鲁工业大学 | Metal atom anchored boron-nitrogen co-doped carbon material and preparation method thereof |
| CN115475641B (en) * | 2022-07-27 | 2023-12-22 | 齐鲁工业大学 | Metal atom anchored boron-nitrogen co-doped carbon material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109806898B (en) | 2021-05-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | High-efficiency electrosynthesis of ammonia with high selectivity under ambient conditions enabled by VN nanosheet array | |
| Liu et al. | Facile ammonia synthesis from electrocatalytic N2 reduction under ambient conditions on N-doped porous carbon | |
| Zhao et al. | Ambient electrosynthesis of ammonia on a biomass-derived nitrogen-doped porous carbon electrocatalyst: contribution of pyridinic nitrogen | |
| Li et al. | Photoinduced charge separation via the double-electron transfer mechanism in nitrogen vacancies g-C3N5/BiOBr for the photoelectrochemical nitrogen reduction | |
| Wang et al. | Recent developments in polymeric carbon nitride-derived photocatalysts and electrocatalysts for nitrogen fixation | |
| Wan et al. | Mo2C-MoO2 heterostructure quantum dots for enhanced electrocatalytic nitrogen reduction to ammonia | |
| Tan et al. | Two-dimensional materials on the rocks: Positive and negative role of dopants and impurities in electrochemistry | |
| Chen et al. | Ambient dinitrogen electrocatalytic reduction for ammonia synthesis | |
| Wang et al. | Self-supported NbSe2 nanosheet arrays for highly efficient ammonia electrosynthesis under ambient conditions | |
| Liu et al. | MoS2 nanodots anchored on reduced graphene oxide for efficient N2 fixation to NH3 | |
| Dubey et al. | Hydrogen generation by water electrolysis using carbon nanotube anode | |
| CN109806898A (en) | A kind of nitrogen co-doped carbon material of boron and the preparation method and application thereof | |
| CN110433846A (en) | A kind of phosphorus doping nitridation cobalt nanowire elctro-catalyst and its preparation method and application | |
| CN108579788A (en) | A kind of compound cobalt vanadium nitride nanowires elctro-catalyst and its preparation method and application | |
| CN107267124A (en) | A kind of nitrogenous graphitized carbon material containing the bimetallic MOFs of Ni/Fe | |
| CN109126850A (en) | A kind of hollow cobalt nickel coated nitrogen-doped carbon nanocomposite and preparation | |
| CN109647408B (en) | Preparation method and application of Co-MOF-based porous composite self-supporting catalyst | |
| CN105470532A (en) | Composite carbon material and preparation method and application thereof | |
| Song et al. | Enhanced electrochemical N2 reduction to NH3 on reduced graphene oxide by tannic acid modification | |
| CN111659394A (en) | Copper-based catalyst and preparation method and application thereof | |
| Liu et al. | Nitrogen-doped carbon quantum dots via a facile reflux assisted polymerization of N-Methyl-Pyrrolidone for hydrogen evolution reaction | |
| CN108611657A (en) | A kind of synthesis and application of the carbon nano-fiber electrochemical catalyst of nitrogenous cobalt molybdenum | |
| CN108615904A (en) | A kind of cobalt acid nickel hollow ball/carbonitride quantum dot composite material and its preparation method and application | |
| CN114032576A (en) | Preparation method of defect nanofiber carbon carrier coupled iron monatomic catalyst | |
| Zhang et al. | Ambient Electrochemical Nitrogen Fixation over a Bifunctional Mo–(O–C2) 4 Site Catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |