CN110364745A - A kind of boron based on ZIF-8, the preparation method of nitrogen co-doped nonmetallic carbon-based oxygen reduction electro-catalyst - Google Patents
A kind of boron based on ZIF-8, the preparation method of nitrogen co-doped nonmetallic carbon-based oxygen reduction electro-catalyst Download PDFInfo
- Publication number
- CN110364745A CN110364745A CN201910481836.0A CN201910481836A CN110364745A CN 110364745 A CN110364745 A CN 110364745A CN 201910481836 A CN201910481836 A CN 201910481836A CN 110364745 A CN110364745 A CN 110364745A
- Authority
- CN
- China
- Prior art keywords
- zif
- doped
- nitrogen
- boron
- preparation
- 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.)
- Pending
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/96—Carbon-based electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Composite Materials (AREA)
- Physics & Mathematics (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
A kind of boron based on ZIF-8, the preparation method of nitrogen co-doped nonmetallic carbon-based oxygen reduction electro-catalyst.The present invention is first, synthesis condition by controlling crystal obtains ZIF-8 presoma, then presoma crystal is mixed with phenyl boric acid small molecule by solvent, stirring, forms evenly dispersed mixing material, is finally carbonized in tube furnace high temperature, obtain black powder carbon material, without further work-up to get arrive boron, nitrogen co-doped nonmetallic carbon-supported catalysts.Advantages of the present invention mainly has: material source is abundant, and cost is relatively low, and prepared material oxygen reduction catalytic activity is high, has good stability, methanol tolerance, has broad application prospects and practical value.
Description
Technical field
The present invention relates to a kind of boron with outstanding electrocatalytic oxidation reduction activation, the preparations of nitrogen co-doped non-metal carbon material
Method relates generally to technical field of material chemistry, fuel cell, cathodic oxygen reduction catalyst field.
Background technique
The rapid development of today's society needs huge energy support, and increasingly serious ecological problem is badly in need of us
Find a kind of energy utilization patterns of efficient green.Fuel cell efficient energy conversion with higher, environmental pollution are small etc. excellent
Point can efficiently solve the contradiction between energy demand and environmental pollution.Currently, the principal element of fuel cell development is restricted
It is that redox reactions (Oxygen Reduction Reaction, ORR) efficiency that cathode occurs is lower.Traditional cathode is urged
The problems such as changing material Pt, that there are reserves is lower, at high price, furthermore poor durability and methanol tolerance toxicity, all become and restrict Pt
The key of large-scale application, to further affect the universal of fuel cell.Therefore, a kind of low in cost, economic height is developed
Effect, with good catalytic activity, the cathode catalysis material of stronger durability and methanol tolerance toxicity develops as fuel cell
Key.
Carbon-based material self-application just relies on its lower cost in terms of the electrode catalyst, intentional catalytic activity and long-term
Durability, receive extensive research and concern.Heteroatom doping can effectively change the intrinsic electrical properties of carbon material
With the appearance structure of material, to effectively improve the catalytic activity of material.Traditional Heteroatom doping carbon material usually usedization
It learns sedimentation to obtain, the cost is relatively high.And hetero atom is directly mixed to the Heteroatom doping carbon materials that carbonization obtains with presoma
Material is difficult to lead to reunion of hetero atom during doping in the microcosmic upper heteroatomic doping of control, cause to imitate during doping
The problems such as rate is lower, and active site is less, and catalyst effect is poor.With metal-organic framework materials (Metal Organic
Frameworks, MOFs) it is presoma, using the regular orderly crystal structure of MOFs material and ordered porous structural abundant,
Hetero atom small molecule can be made to be sufficiently mixed during pretreated uniformly, be evenly distributed, have to obtain hetero atom
The Heteroatom doping carbon material of abundant active site and large specific surface area.ZIF-8 is that one kind is cheap and easy to get, has compared with high stable
Property crystalline material, furthermore the lower Zn of boiling point is easy to remove in carbonisation, formed porous carbon materials, be conducive to carbon material
Active raising.Nitrogenous ligand abundant makes the carbon material obtained after talking have active site abundant.Currently, common
Nonmetallic heteroatoms are by B, N, S, P etc..It is the porous carbon nanomaterial of precursor preparation Heteroatom doping by extensive using ZIF-8
Concern, but use ZIF-8 for presoma, phenyl boric acid is boron source, prepares B, and N codope porous carbon materials are simultaneously applied to electro-catalysis
The case of oxygen reduction catalyst has not yet to see report.
The present invention uses ZIF-8 material as presoma, using phenyl boric acid as boron source, in atmosphere of inert gases high temperature carbon
Change, is prepared for a kind of B, the porous carbon materials of N codope.Obtained material has benefited from the doping of boron, so that the pyridine in material
The content of nitrogen and graphite nitrogen gets a promotion, with preferable catalytic activity, and what porous nitrogenous presoma ZIF-8 made
Carbon material has cellular structure abundant, biggish specific surface area etc., and more active site is conducive in catalytic reaction process
The transmitting of substance and contact with reaction site.
By electro-chemical test, the carbon material of this method preparation has good hydrogen reduction potential, and outstanding is steady in a long-term
Property and stronger methanol tolerance toxicity, have a good application prospect.
Summary of the invention
In view of the above-mentioned problems, it is presoma that the present invention, which provides a kind of ZIF-8, boron, nitrogen co-doped electrocatalytic oxidation reduction is porous
Carbon material catalyst prepares B using phenyl boric acid as boron source for presoma using ZIF-8 by way of high temperature cabonization, N is co-doped with
Miscellaneous porous carbon materials catalyst.
The technical scheme is that a kind of boron based on ZIF-8, nitrogen co-doped nonmetallic carbon-based oxygen reduction electro-catalyst
Preparation method, it is specific the preparation method is as follows:
Step 1: the preparation of presoma ZIF-8 material:
The zinc nitrate hexahydrate for weighing 0.117g, is dissolved in the distilled water of 10mL, and ultrasound makes it completely dissolved, and obtains six
Nitric hydrate zinc solution；The 2-methylimidazole for separately weighing 2.270g, is dissolved in the distilled water of 90mL, and ultrasound keeps it completely molten
Solution, obtains 2-methylimidazole solution；Two kinds of solution obtained above is mixed, it is molten to obtain ZIF-8 by reaction 12h at room temperature
Obtained ZIF-8 solution is placed in a centrifuge centrifugation 8min, obtained miscellaneous containing aqueous solvent and zinc nitrate, 2-methylimidazole by liquid
The ZIF-8 solid of matter, by the ZIF-8 solid methanol supersound washing 3-5 containing aqueous solvent and zinc nitrate, 2-methylimidazole impurity
It is secondary, dry 12h in 60 DEG C of vacuum ovens；The ZIF-8 solid of zinc nitrate Yu 2-methylimidazole impurity is dispelled；It will be above-mentioned
What is obtained has dispelled the ZIF-8 solid of zinc nitrate and 2-methylimidazole, and activation 2h is vacuumized at 200 DEG C；It is pure to obtain 0.2g
ZIF-8 solid；
Step 2: the preparation of catalyst precursor:
It weighs the phenyl boric acid solid of 0.008g and above-mentioned obtains the pure ZIF-8 solid of 0.2g；Above two solid is placed in
In 100mL methanol solution, at room temperature, stirring 12h obtains the ZIF-8 solution doped with phenyl boric acid, in centrifuge, will obtain
The ZIF-8 solution doped with phenyl boric acid revolving speed be 1000rpm centrifugal speed under, be centrifuged 20min, 50 DEG C vacuum drying
12h；Obtain the ZIF-8 presoma containing phenyl boric acid；
Step 3: boron, the preparation of nitrogen co-doped electrocatalytic oxidation reduction porous carbon materials:
The above-mentioned ZIF-8 presoma obtained containing phenyl boric acid is put into tube furnace, in nitrogen atmosphere, per minute with 5 DEG C
1000 DEG C of constant temperature are warming up to, and after being maintained at temperature 2h, is cooled to room temperature per minute with 5 DEG C, boron, nitrogen co-doped non-gold are obtained
Belong to carbon-based oxygen reduction electro-catalyst.
The mass ratio of the zinc nitrate hexahydrate and 2-methylimidazole is 1:100~10:100.
The room temperature is 10~30 DEG C, and being stirred to react the time is 8~14h.
The mass ratio of the ZIF-8 and phenyl boric acid is 100:1~100:10, and the reaction time is 8~16h.
The constant temperature is 900~1000 DEG C.
Prepared catalysis material is for fuel battery negative pole hydrogen reduction catalysis reaction.
Using ZIF-8 as presoma, phenyl boric acid is boron source, is carbonized under high temperature inert gas environment, and boron is prepared, nitrogen co-doped
Porous carbon is as electrocatalytic oxidation reducing catalyst；The surface area and conductive capability of material are not only improved, it is more effective to improve
The electro-catalysis ability of material shows that material has lower hydrogen reduction potential and higher electric current close by electro-chemical test
Degree, is a kind of catalysis material of efficient stable.
Boron prepared by the present invention, nitrogen co-doped nonmetallic carbon-supported catalysts, be it is a kind of have good catalytic activity with it is durable
The catalyst of property.ZIF-8 ordered porous crystal structure, so that material has biggish specific surface area in the carbonized.It is nitrogenous rich
Ligand rich in sequence generates the equally distributed material of active site after being conducive to carbonization, improves the catalytic activity of material.Without gold
The phenomenon that active site loss will not occur in catalytic process in the carbon-based material of category, be a kind of elctro-catalyst of stability and high efficiency.
The doping of boron element promotes material to generate more oxygen reduction activity positions so that the nitrogen content of material is promoted
Point, positively charged boron also effectively raise the wettability of material and to oxygen other than improving the conductive capability of material
Adsorption capacity.
All raw materials are all from a wealth of sources, take water as a solvent, and green non-pollution is cheap and easy to get, the preparation process of catalyst
Also simple and easy, it is suitble to large-scale production, compared to materials such as traditional Pt, has more price advantage.
The beneficial effects of the present invention are: operation is simple for the invention patent, raw material sources are extensive.It is prepared using the present invention
Boron, nitrogen co-doped nonmetallic carbon-supported catalysts have excellent catalytic activity and long-time stability.Pt can be replaced to be used as to urge
Change material and is applied to fuel cell.Various mobile electronic products, such as mobile phone can be applied to using fuel cell produced by the present invention,
Tablet computer, digital camera etc..
Detailed description of the invention
Fig. 1 is boron obtained by the present invention, nitrogen co-doped nonmetallic carbon-supported catalysts transmission electron microscope picture schematic diagram,
Fig. 2 is boron obtained by the present invention, and the nitrogen adsorption-that the BET of nitrogen co-doped nonmetallic carbon-supported catalysts is tested is de-
Attached curve and pore size distribution curve schematic diagram.
(a) is boron obtained by the present invention, the x-ray photoelectron spectroscopy (XPS) of nitrogen co-doped nonmetallic carbon-supported catalysts in Fig. 3
The total energy spectrum schematic diagram of test；It (b) is boron, the N1s high-resolution x-ray photoelectron spectroscopy of nitrogen co-doped nonmetallic carbon-supported catalysts
Schematic diagram；
The boron that Fig. 4 is, the Raman displacement spectra of nitrogen co-doped nonmetallic carbon-supported catalysts, which illustrates, to be intended to；
(a) is present invention gained boron in Fig. 5, and nitrogen co-doped nonmetallic carbon-supported catalysts obtain linear under different rotating speeds
Scan volt-ampere curve；It (b) is gained boron, the K-L curve graph of nitrogen co-doped nonmetallic carbon-supported catalysts；
Fig. 6 is boron obtained by the present invention, the accelerated ageing test schematic diagram of nitrogen co-doped nonmetallic carbon-supported catalysts.
Specific embodiment
To further understand the present invention, in conjunction with attached drawing, the present invention will be further described with embodiment, but not with any
Mode limits the present invention.
A kind of boron based on ZIF-8, the preparation method of nitrogen co-doped nonmetallic carbon-based oxygen reduction electro-catalyst are specific to make
Preparation Method is as follows:
Step 1: the preparation of presoma ZIF-8 material:
The zinc nitrate hexahydrate for weighing 0.117g, is dissolved in the distilled water of 10mL, and ultrasound makes it completely dissolved, and obtains six
Nitric hydrate zinc solution；The 2-methylimidazole for separately weighing 2.270g, is dissolved in the distilled water of 90mL, and ultrasound keeps it completely molten
Solution, obtains 2-methylimidazole solution；Two kinds of solution obtained above is mixed, it is molten to obtain ZIF-8 by reaction 12h at room temperature
Obtained ZIF-8 solution is placed in a centrifuge centrifugation 8min, obtained miscellaneous containing aqueous solvent and zinc nitrate, 2-methylimidazole by liquid
The ZIF-8 solid of matter, by the ZIF-8 solid methanol supersound washing 3-5 containing aqueous solvent and zinc nitrate, 2-methylimidazole impurity
It is secondary, dry 12h in 60 DEG C of vacuum ovens；The ZIF-8 solid of zinc nitrate Yu 2-methylimidazole impurity is dispelled；It will be above-mentioned
What is obtained has dispelled the ZIF-8 solid of zinc nitrate and 2-methylimidazole, and activation 2h is vacuumized at 200 DEG C；It is pure to obtain 0.2g
ZIF-8 solid；
Step 2: the preparation of catalyst precursor:
It weighs the phenyl boric acid solid of 0.008g and above-mentioned obtains the pure ZIF-8 solid of 0.2g；Above two solid is placed in
In 100mL methanol solution, at room temperature, stirring 12h obtains the ZIF-8 solution doped with phenyl boric acid, in centrifuge, will obtain
The ZIF-8 solution doped with phenyl boric acid revolving speed be 1000rpm centrifugal speed under, be centrifuged 20min, 50 DEG C vacuum drying
12h；Obtain the ZIF-8 presoma containing phenyl boric acid；
Step 3: boron, the preparation of nitrogen co-doped electrocatalytic oxidation reduction porous carbon materials:
The above-mentioned ZIF-8 presoma obtained containing phenyl boric acid is put into tube furnace, in nitrogen atmosphere, per minute with 5 DEG C
1000 DEG C of constant temperature are warming up to, and after being maintained at temperature 2h, is cooled to room temperature per minute with 5 DEG C, boron, nitrogen co-doped non-gold are obtained
Belong to carbon-based oxygen reduction electro-catalyst.
The mass ratio of the zinc nitrate hexahydrate and 2-methylimidazole is 1:100~10:100.
The room temperature is 10~30 DEG C, and being stirred to react the time is 8~14h.
The mass ratio of the ZIF-8 and phenyl boric acid is 100:1~100:10, and the reaction time is 8~16h.
The constant temperature is 900~1000 DEG C.
Prepared catalysis material is for fuel battery negative pole hydrogen reduction catalysis reaction.
Specific embodiment 1:
Step 1: the preparation of presoma ZIF-8 material:
The zinc nitrate hexahydrate for weighing 0.117g, is dissolved in the distilled water of 10mL, and ultrasound makes it completely dissolved, and obtains six
Nitric hydrate zinc solution；The 2-methylimidazole for separately weighing 2.270g, is dissolved in the distilled water of 90mL, and ultrasound keeps it completely molten
Solution, obtains 2-methylimidazole solution；Two kinds of solution obtained above is mixed, it is molten to obtain ZIF-8 by reaction 12h at room temperature
Obtained ZIF-8 solution is placed in a centrifuge centrifugation 8min, obtained miscellaneous containing aqueous solvent and zinc nitrate, 2-methylimidazole by liquid
The ZIF-8 solid of matter, by the ZIF-8 solid methanol supersound washing 3-5 containing aqueous solvent and zinc nitrate, 2-methylimidazole impurity
It is secondary, dry 12h in 60 DEG C of vacuum ovens；The ZIF-8 solid of zinc nitrate Yu 2-methylimidazole impurity is dispelled；It will be above-mentioned
The ZIF-8 solid for having been dispelled zinc nitrate and 2-methylimidazole vacuumizes activation 2h at 200 DEG C；Obtain the pure ZIF-8 of 0.2g
Solid；
Step 2: the preparation of catalyst precursor:
It weighs the phenyl boric acid solid of 0.008g and above-mentioned obtains the pure ZIF-8 solid of 0.2g；Above two solid is placed in
In 100mL methanol solution, at room temperature, stirring 12h obtains the ZIF-8 solution doped with phenyl boric acid；It will obtain doped with benzene
The ZIF-8 solution of boric acid is placed in a centrifuge, and in the case where revolving speed is the centrifugal speed of 1000rpm, is centrifuged 20min, 50 DEG C of vacuum are dry
Dry 12h；Obtain the ZIF-8 presoma containing phenyl boric acid；
Step 3: boron, the preparation of nitrogen co-doped electrocatalytic oxidation reduction porous carbon materials:
The above-mentioned ZIF-8 presoma obtained containing phenyl boric acid is put into tube furnace, in nitrogen atmosphere, per minute with 5 DEG C
1000 DEG C of constant temperature are warming up to, and is maintained at temperature 2h, is cooled to room temperature per minute with 5 DEG C, boron is obtained, it is nitrogen co-doped nonmetallic
Carbon-based oxygen reduction electro-catalyst；
Specific embodiment 2:
Step 1: the preparation of ZIF-8 presoma:
According to the method and condition preparation of step 1 in embodiment 1；
Step 2: the preparation of catalyst precursor:
According to the method and condition preparation of step 2 in embodiment 1；
Step 3: boron, the preparation of nitrogen co-doped carbon material
The persursor material that above-mentioned steps two obtain is put into tube furnace, in nitrogen atmosphere, is warming up to 5 DEG C/min
950 DEG C, and it is maintained at temperature 2h, it is cooled to room temperature per minute with 5 DEG C, obtains boron, nitrogen co-doped nonmetallic carbon-based hydrogen reduction
Elctro-catalyst；
Specific embodiment 3:
Step 1: the preparation of ZIF-8 presoma
According to the method and condition preparation of step 1 in embodiment 1.；
Step 2: the preparation of catalyst precursor
According to the method and condition preparation of step 2 in embodiment 1；
Step 3: boron, the preparation of nitrogen co-doped carbon material:
The persursor material that above-mentioned steps two obtain is put into tube furnace, in nitrogen atmosphere, is warming up to 5 DEG C/min
1000 DEG C, and it is maintained at temperature 2h, it is cooled to room temperature per minute with 5 DEG C, obtains boron, nitrogen co-doped nonmetallic carbon-based hydrogen reduction
Elctro-catalyst.
Boron prepared by the present invention, nitrogen co-doped nonmetallic carbon-supported catalysts, be it is a kind of have good catalytic activity with it is durable
The catalyst of property.ZIF-8 ordered porous crystal structure, so that material has biggish specific surface area in the carbonized.It is nitrogenous rich
Ligand rich in sequence generates the equally distributed material of active site after being conducive to carbonization, improves the catalytic activity of material.Without gold
The phenomenon that active site loss will not occur in catalytic process in the carbon-based material of category, be a kind of elctro-catalyst of stability and high efficiency.
The doping of boron element promotes material to generate more oxygen reduction activity positions so that the nitrogen content of material is promoted
Point, positively charged boron also effectively raise the wettability of material and to oxygen other than improving the conductive capability of material
Adsorption capacity.
All raw materials are all from a wealth of sources, take water as a solvent, and green non-pollution is cheap and easy to get, the preparation process of catalyst
Also simple and easy, it is suitble to large-scale production, compared to materials such as traditional Pt, has more price advantage.
Wherein, Fig. 1 is present invention gained boron, nitrogen co-doped nonmetallic carbon-supported catalysts transmission electron microscope photo.It can be seen that
After high temperature cabonization, the original pattern of crystal is destroyed, the boron of generation, and nitrogen co-doped carbon material has good porous structure.
Fig. 2 is present invention gained boron, and the nitrogen adsorption-that the BET of nitrogen co-doped nonmetallic carbon-supported catalysts is tested is de-
Attached curve and pore size distribution curve.By BET theoretical calculation, the specific surface area of obtained BNC-1000-3 is 1181.2m2*g-1,
Pore volume is 1.01cm3*g-1.From Fig. 2 (a) it can be seen that IV type thermoisopleth is presented in the nitrogen adsorption of material-desorption curve, have
Apparent H4 type hysteresis loop shows that material has a large amount of mesoporous and macroporous structure, and Fig. 2 (b) is it can be seen that material is a kind of
Mesoporous with micropore, the multistage porous material of macropore can effectively improve electron-transport, charge dispersion, the speed of substance transmitting
Rate.
Fig. 3 (a) is present invention gained boron, and the x-ray photoelectron spectroscopy (XPS) of nitrogen co-doped nonmetallic carbon-supported catalysts is surveyed
The total energy spectrum of examination, Fig. 3 (b) are 3 boron of embodiment, the N1s high-resolution x-ray photoelectron energy of nitrogen co-doped nonmetallic carbon-supported catalysts
Spectrum.From Fig. 3 (a) as can be seen that there is the peak XPS of B1s in material, show that boron atom is successfully doped in carbon material.Fig. 3
(b) it can be seen that containing more there is hydrogen reduction to urge active graphite nitrogen component in material.
Fig. 4 is the obtained boron of the present invention, and the Raman of nitrogen co-doped nonmetallic carbon-supported catalysts is displaced spectrogram.It can be seen that material
Material is in 1340cm-1With 1590cm-1Nearby there is apparent Raman displacement peak, it can be seen that the material of preparation stone with higher
Blackization degree.
Fig. 5 (a) is present invention gained boron, and what nitrogen co-doped nonmetallic carbon-supported catalysts obtained under different rotating speeds linearly sweeps
Retouch volt-ampere curve.Fig. 5 (b) is 3 gained boron of embodiment, the K-L curve of nitrogen co-doped nonmetallic carbon-supported catalysts.It can therefrom see
Out, the electron transfer number of material is about 3.7 or so, illustrates boron, nitrogen co-doped nonmetallic carbon-supported catalysts catalysis with higher
Selectivity, hydrogen reduction catalytic pathway is mainly based on four electronic processes.
Fig. 6 is present invention gained boron, the accelerated ageing test of nitrogen co-doped nonmetallic carbon-supported catalysts, it can be seen that material
After 10000cycles CV sweep test, it is still able to maintain higher catalytic activity, half wave potential only declines 8mV, limit diffusion
Current density decline 4.25% illustrates that material has preferable catalytic stability.
Operation of the present invention is simple and easy, and raw material sources are extensive.It is nitrogen co-doped nonmetallic carbon-based using boron prepared by the present invention
Catalyst has excellent catalytic activity and long-time stability.Pt can be replaced to be applied to fuel cell as catalysis material.It adopts
It can be applied to various mobile electronic products, such as mobile phone, tablet computer, digital camera etc. with fuel cell produced by the present invention.
Claims (6)
1. a kind of boron based on ZIF-8, the preparation method of nitrogen co-doped nonmetallic carbon-based oxygen reduction electro-catalyst, feature exist
In: its it is specific the preparation method is as follows:
Step 1: the preparation of presoma ZIF-8 material:
The zinc nitrate hexahydrate for weighing 0.117g, is dissolved in the distilled water of 10mL, and ultrasound makes it completely dissolved, and obtains six hydrations
Zinc nitrate solution；The 2-methylimidazole for separately weighing 2.270g, is dissolved in the distilled water of 90mL, ultrasound makes it completely dissolved, and obtains
To 2-methylimidazole solution；Two kinds of solution obtained above is mixed, 12h is reacted at room temperature and obtains ZIF-8 solution, will
To ZIF-8 solution be placed in a centrifuge centrifugation 8min, obtain the ZIF- containing aqueous solvent and zinc nitrate, 2-methylimidazole impurity
8 solids, by ZIF-8 solid methanol supersound washing 3-5 times containing aqueous solvent and zinc nitrate, 2-methylimidazole impurity, 60 DEG C
Dry 12h in vacuum oven；The ZIF-8 solid of zinc nitrate Yu 2-methylimidazole impurity is dispelled；It will be obtained above
The ZIF-8 solid for having dispelled zinc nitrate and 2-methylimidazole vacuumizes activation 2h at 200 DEG C；It is solid to obtain the pure ZIF-8 of 0.2g
Body；
Step 2: the preparation of catalyst precursor:
It weighs the phenyl boric acid solid of 0.008g and above-mentioned obtains the pure ZIF-8 solid of 0.2g；Above two solid is placed in 100mL
In methanol solution, at room temperature, stirring 12h obtains the ZIF-8 solution doped with phenyl boric acid, in centrifuge, mixes what is obtained
The miscellaneous ZIF-8 solution for having phenyl boric acid is centrifuged 20min, 50 DEG C of vacuum drying 12h in the case where revolving speed is the centrifugal speed of 1000rpm；?
To the ZIF-8 presoma containing phenyl boric acid；
Step 3: boron, the preparation of nitrogen co-doped electrocatalytic oxidation reduction porous carbon materials:
The above-mentioned ZIF-8 presoma obtained containing phenyl boric acid is put into tube furnace, in nitrogen atmosphere, with 5 DEG C of heatings per minute
It to 1000 DEG C of constant temperature, and after being maintained at temperature 2h, is cooled to room temperature per minute with 5 DEG C, obtains boron, nitrogen co-doped non-metal carbon
Base oxygen reduction electro-catalyst.
2. a kind of boron based on ZIF-8 according to claim 1, nitrogen co-doped nonmetallic carbon-based oxygen reduction electro-catalyst
Preparation method, which is characterized in that the mass ratio of the zinc nitrate hexahydrate and 2-methylimidazole is 1:100~10:100.
3. a kind of boron based on ZIF-8 according to claim 1, nitrogen co-doped nonmetallic carbon-based oxygen reduction electro-catalyst
Preparation method, which is characterized in that the room temperature is 10~30 DEG C, and being stirred to react the time is 8~14h.
4. a kind of boron based on ZIF-8 according to claim 1, nitrogen co-doped nonmetallic carbon-based oxygen reduction electro-catalyst
Preparation method, which is characterized in that the mass ratio of the ZIF-8 and phenyl boric acid be 100:1~100:10, the reaction time be 8~
16h。
5. a kind of boron based on ZIF-8 according to claim 1, nitrogen co-doped nonmetallic carbon-based oxygen reduction electro-catalyst
Preparation method, which is characterized in that the constant temperature is 900~1000 DEG C.
6. a kind of boron based on ZIF-8 according to claim 1, nitrogen co-doped nonmetallic carbon-based oxygen reduction electro-catalyst
Preparation method, it is characterised in that: prepared catalysis material for fuel battery negative pole hydrogen reduction catalysis reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910481836.0A CN110364745A (en) | 2019-06-04 | 2019-06-04 | A kind of boron based on ZIF-8, the preparation method of nitrogen co-doped nonmetallic carbon-based oxygen reduction electro-catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910481836.0A CN110364745A (en) | 2019-06-04 | 2019-06-04 | A kind of boron based on ZIF-8, the preparation method of nitrogen co-doped nonmetallic carbon-based oxygen reduction electro-catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110364745A true CN110364745A (en) | 2019-10-22 |
Family
ID=68215008
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910481836.0A Pending CN110364745A (en) | 2019-06-04 | 2019-06-04 | A kind of boron based on ZIF-8, the preparation method of nitrogen co-doped nonmetallic carbon-based oxygen reduction electro-catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110364745A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111613801A (en) * | 2020-05-07 | 2020-09-01 | 山西大学 | Boron-nitrogen-phosphorus ternary doped metal-free carbon material and preparation method and application thereof |
| CN111916769A (en) * | 2020-08-20 | 2020-11-10 | 浙江工业大学 | Preparation method of Cu-doped hollow hexagonal ZIF-8 material for zinc-air battery |
| CN112164807A (en) * | 2020-09-30 | 2021-01-01 | 华中科技大学 | Porous nitrogen and boron co-doped carbon-based oxygen reduction catalyst and preparation method and application thereof |
| CN112374488A (en) * | 2020-11-17 | 2021-02-19 | 山东大学 | Preparation method of hollow boron-nitrogen co-doped carbon nanospheres with high boron content |
| CN112820886A (en) * | 2020-12-29 | 2021-05-18 | 北京化工大学 | Three-dimensional grading porous nonmetal carbon-based material and preparation method and application thereof |
| CN112909275A (en) * | 2021-03-29 | 2021-06-04 | 华中科技大学 | Sp-rich food3Metal-free carbon-based catalyst of hybrid carbon and preparation method thereof |
| CN114395768A (en) * | 2022-01-21 | 2022-04-26 | 辽宁大学 | Co/B/N Co-doped carbon electrocatalyst and preparation method and application thereof |
| CN114570351A (en) * | 2022-03-02 | 2022-06-03 | 东北林业大学 | Boron-phosphorus co-doped metal-free carbon-based catalytic material and preparation method and application thereof |
| CN115138390A (en) * | 2022-08-19 | 2022-10-04 | 浙江理工大学 | Boron-nitrogen CO-doped hollow nano carbon material, preparation method thereof and application thereof in photocatalysis of CO 2 Use in cycloaddition |
| CN115991458A (en) * | 2023-02-27 | 2023-04-21 | 中国科学院生态环境研究中心 | Defect-rich spherical boron nitride assembled by nano-flakes as well as preparation method and application thereof |
| CN114430047B (en) * | 2020-09-24 | 2024-04-02 | 中国石油化工股份有限公司 | Carbon material, platinum-carbon catalyst, and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103508434A (en) * | 2012-06-28 | 2014-01-15 | 中国科学院大连化学物理研究所 | Preparation method of boron/nitrogen-doped microporous carbon material |
| CN105552385A (en) * | 2016-03-16 | 2016-05-04 | 湘潭大学 | Boron-doped carbon material and preparation method and application thereof |
| CN106040182A (en) * | 2016-07-25 | 2016-10-26 | 江苏大学 | Method for preparing carbon foam adsorbents modified by phenylboronic acid type metal organic framework materials |
| CN107029694A (en) * | 2017-05-23 | 2017-08-11 | 中国石油大学(北京) | One kind doping carbon material and preparation method thereof |
-
2019
- 2019-06-04 CN CN201910481836.0A patent/CN110364745A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103508434A (en) * | 2012-06-28 | 2014-01-15 | 中国科学院大连化学物理研究所 | Preparation method of boron/nitrogen-doped microporous carbon material |
| CN105552385A (en) * | 2016-03-16 | 2016-05-04 | 湘潭大学 | Boron-doped carbon material and preparation method and application thereof |
| CN106040182A (en) * | 2016-07-25 | 2016-10-26 | 江苏大学 | Method for preparing carbon foam adsorbents modified by phenylboronic acid type metal organic framework materials |
| CN107029694A (en) * | 2017-05-23 | 2017-08-11 | 中国石油大学(北京) | One kind doping carbon material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| FEI HAO: ""Synthesis of high-concentration B and N co-doped porous carbon polyhedral and their supercapacitive properties"", 《RSC ADVANCES》 * |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111613801A (en) * | 2020-05-07 | 2020-09-01 | 山西大学 | Boron-nitrogen-phosphorus ternary doped metal-free carbon material and preparation method and application thereof |
| CN111916769A (en) * | 2020-08-20 | 2020-11-10 | 浙江工业大学 | Preparation method of Cu-doped hollow hexagonal ZIF-8 material for zinc-air battery |
| CN114430047B (en) * | 2020-09-24 | 2024-04-02 | 中国石油化工股份有限公司 | Carbon material, platinum-carbon catalyst, and preparation method and application thereof |
| CN112164807A (en) * | 2020-09-30 | 2021-01-01 | 华中科技大学 | Porous nitrogen and boron co-doped carbon-based oxygen reduction catalyst and preparation method and application thereof |
| CN112374488B (en) * | 2020-11-17 | 2022-07-19 | 山东大学 | Preparation method of hollow boron-nitrogen co-doped carbon nanospheres with high boron content |
| CN112374488A (en) * | 2020-11-17 | 2021-02-19 | 山东大学 | Preparation method of hollow boron-nitrogen co-doped carbon nanospheres with high boron content |
| CN112820886A (en) * | 2020-12-29 | 2021-05-18 | 北京化工大学 | Three-dimensional grading porous nonmetal carbon-based material and preparation method and application thereof |
| CN112909275A (en) * | 2021-03-29 | 2021-06-04 | 华中科技大学 | Sp-rich food3Metal-free carbon-based catalyst of hybrid carbon and preparation method thereof |
| CN114395768A (en) * | 2022-01-21 | 2022-04-26 | 辽宁大学 | Co/B/N Co-doped carbon electrocatalyst and preparation method and application thereof |
| CN114395768B (en) * | 2022-01-21 | 2023-11-10 | 辽宁大学 | Co/B/N Co-doped carbon electrocatalyst and preparation method and application thereof |
| CN114570351A (en) * | 2022-03-02 | 2022-06-03 | 东北林业大学 | Boron-phosphorus co-doped metal-free carbon-based catalytic material and preparation method and application thereof |
| CN114570351B (en) * | 2022-03-02 | 2023-12-29 | 东北林业大学 | Boron-phosphorus co-doped metal-free carbon-based catalytic material and preparation method and application thereof |
| CN115138390A (en) * | 2022-08-19 | 2022-10-04 | 浙江理工大学 | Boron-nitrogen CO-doped hollow nano carbon material, preparation method thereof and application thereof in photocatalysis of CO 2 Use in cycloaddition |
| CN115138390B (en) * | 2022-08-19 | 2023-10-13 | 浙江理工大学 | Boron-nitrogen CO-doped hollow nano carbon material, preparation method thereof and photocatalytic CO (carbon monoxide) 2 Application in cycloaddition |
| CN115991458A (en) * | 2023-02-27 | 2023-04-21 | 中国科学院生态环境研究中心 | Defect-rich spherical boron nitride assembled by nano-flakes as well as preparation method and application thereof |
| CN115991458B (en) * | 2023-02-27 | 2024-05-31 | 中国科学院生态环境研究中心 | Defect-rich spherical boron nitride assembled by nano-flakes as well as preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110364745A (en) | A kind of boron based on ZIF-8, the preparation method of nitrogen co-doped nonmetallic carbon-based oxygen reduction electro-catalyst | |
| CN110350211B (en) | Preparation method of ZIF-8 derived N, S-codoped non-metallic carbon-based nano oxygen reduction electrocatalyst | |
| CN110911697B (en) | Transition metal/nitrogen-doped porous carbon nanosphere electrocatalyst and preparation method thereof | |
| CN111276708B (en) | Fe/N/C oxygen reduction catalyst based on MOF-5 and preparation method and application thereof | |
| CN105170169B (en) | A kind of nitrogen-doped graphene iron-based nano-particles reinforcement type catalyst and preparation method thereof | |
| CN109065897B (en) | Phosphorus-doped porous carbon-coated cobaltosic oxide oxygen reduction catalyst and preparation method and application thereof | |
| CN107887613B (en) | Oxygen reduction electrode based on three-dimensional net-shaped nitrogen, phosphorus and sulfur co-doped porous carbon material, and preparation method and application thereof | |
| CN110534755B (en) | Zinc-based metal organic framework material and preparation method and application of iron-nitrogen co-doped carbon-based oxygen reduction electrocatalyst thereof | |
| CN109841854A (en) | A kind of nitrogen-doped carbon-supported antozone reducing catalyst and preparation method thereof | |
| CN111384407A (en) | Preparation method of metal monoatomic-dispersed ordered mesoporous carbon spheres | |
| CN108486605A (en) | A kind of carbon coating selenizing nickel cobalt nano material and preparation method thereof with excellent electrolysis water performance | |
| CN109728311B (en) | Metal organic framework compound hollow microsphere loaded with iron cobalt sulfide | |
| CN103495432A (en) | Method for preparing efficient stable fuel cell catalyst | |
| CN112827504B (en) | Method for preparing pyridine or pyrrole iron-nitrogen site catalyst, product and application thereof | |
| CN110721713B (en) | Mo 2 C catalytic material and preparation method and application thereof | |
| CN110048134A (en) | A kind of universality method preparing porous nitrogen fluorine codope carbon oxygen reduction catalyst | |
| CN114068963B (en) | Preparation method and application of transition metal and compound thereof anchored nitrogen-doped carbon catalyst | |
| CN110756188A (en) | Preparation method of three-dimensional carbon network supported FeCo bifunctional oxygen catalyst | |
| CN106848334A (en) | A kind of oxygen reduction catalyst containing pyrrole radicals tetrazine ring and preparation method thereof | |
| CN108649237B (en) | Gel pyrolysis-based cobalt-nitrogen doped carbon composite material and preparation method and application thereof | |
| CN110504456A (en) | It is a kind of based on nitrogen oxygen doping ball/piece porous carbon materials oxygen reduction electrode and its preparation method and application | |
| CN112652780A (en) | Fe/Fe3Preparation method of C nano-particle loaded porous nitrogen-doped carbon-based oxygen reduction catalyst | |
| CN114892202B (en) | MOFs derived porous carbon electrocatalyst and preparation method and application thereof | |
| CN103316679A (en) | Preparation method of ordered mesoporous non-noble metal-nitrogen-graphitized carbon material | |
| CN113381034B (en) | Preparation method and application of polypyrrole gel loaded copper-phosphorus atom composite material |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20191022 |