CN106955725A - The preparation and the application as electrochemical catalyst of a kind of N, S codope graphitized carbon material - Google Patents
The preparation and the application as electrochemical catalyst of a kind of N, S codope graphitized carbon material Download PDFInfo
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- CN106955725A CN106955725A CN201710089359.4A CN201710089359A CN106955725A CN 106955725 A CN106955725 A CN 106955725A CN 201710089359 A CN201710089359 A CN 201710089359A CN 106955725 A CN106955725 A CN 106955725A
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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- 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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention provides a kind of N, the preparation method of S codope graphitized carbon materials is by bovine serum albumin（BSA）It is dissolved in poly ion liquid in N, N dimethylformamides and obtains transparent uniform solution；Again by solution coating on the glass sheet, through AMMONIA TREATMENT deprotonation after drying, obtain with porous, height ionomer precursor film material, further carbonization can be prepared by the N with excellent electro catalytic activity, S codope graphitized carbon materials to the membrane material.Electro-chemical test shows that the carbon material shows excellent catalytic performance in HER and OER, and it is in 10 mA/cm2Current density under overpotential be respectively 165 mV and 460 mV, the value is higher than the non-metal catalyst reported at present.
Description
Background technology
Hydrogen is a kind of renewable energy source carrier of cleaning, therefore is a kind of preferable fossil energy substitute.Water-splitting is held
Continuous production hydrogen is an attractive solution, but needs elctro-catalyst efficient, steady in a long-term.It is used as benchmark electro-catalysis
Agent, platinum carbon is in evolving hydrogen reaction（HER）In show very excellent catalytic activity, but its high cost and scarcity are limited
Its extensive use in actual industrial.Therefore, people have been opened to a variety of non-precious metal catalysts, such as CoP/CNTs,
Mo2C/MoB, MoS2/ RGO, CoPS, CoOx, Ni2P and their alloy etc., but these non-precious metal catalysts also have
The shortcomings of use environment limitation, low activity, catalyst loss.
Research recently finds that the graphitized carbon of Heteroatom doping has preferable HER catalytic activity, and in acid and alkalescence
Under the conditions of all there is excellent stability, therefore, explore becomes current electricity with the preparation method of high catalytic activity carbon material
One of hot research direction of chemical catalysis field.That reports at present is all based on graphene, carbon for the carbon-based catalysis materials of HER
Nanotube and C3N4Deng these material preparation process complexity, low yield.
The content of the invention
The purpose of the present invention is that there is provided a kind of new N, S codope graphitization carbon materials the problem of presence for prior art
Material；
It is a further object of the present invention to provide the above-mentioned new N of one kind, the preparation method of S codope graphitized carbon materials；
It is a further aim of the invention the above-mentioned new N of research, the electro catalytic activity of S codope graphitized carbon materials, and make
Evolving hydrogen reaction is applied to for catalyst（HER）In.
First, N, S codope graphitized carbon material
The preparation of N of the present invention, S codope graphitized carbon material, is by poly ion liquid PCMVImTf2N and bovine serum albumin BSA
With 1:1~11:1 mass ratio is dissolved in DMF, obtains the transparent uniform solution that total concentration is 46 ~ 278 g/L；The solution is coated again
On the glass sheet, the ethanol solution of 0.4 ~ 0.5wt% ammonia is immersed in after baking oven 2 ~ 3 hours, obtains BSA@PCMVImTf2The porous forerunners of N
Body film；Then by BSA@PCMVImTf2The porous precursor films of N are put into tube furnace, are warming up to 800 ~ 1000 DEG C（Heating rate is
With 10 DEG C/min）, reach and kept for 1 ~ 1.5 hour after target temperature；Room temperature is naturally cooling to, BSA@PCMVImTf are produced2N is answered
Close membrane material --- N, S codope graphitized carbon material.
2nd, N, S codope graphitized carbon material structure and morphology are characterized
1st, scanning electron microscope image（SEM）
The surface topography of material is observed with SEM first, as shown in Figure 1：Material surface is clear that poroid
Pattern, can also see that from the figure of amplification material surface there is micropore, a variety of pore structures such as mesoporous and macropore.These loose structures
The active surface area of larger, accessible property is provided for material, at the same time some macropores on surface and internal micro-
The three-dimensional network of interconnection can be formed between hole, so as to expand transport channel, to accelerate diffusion and significant promotion exchange efficiency.
2nd, high resolution transmission electron microscopy（HRTEM）
Fig. 2 is BSA@PCMVImTf under different temperatures2High resolution transmission electron microscopy after N carbonizations（HRTEM）,（1）C-800
℃；（2）C-900℃；（3）C-1000℃；（4）Partial enlarged drawing under C-1000 material 50nm yardsticks.Figure（1）Show C-
800 graphite linings, showing it has certain order region.From figure（2）It can more find occur monocrystalline atom packing in whole film.Figure
（3）With more regular graphite-structure, with less lattice defect.We can observe in these figures by many shells and
The onion shape concentric graphitic nanostructured of the lattice formation of hollow form, as such a form of the increase of temperature is more and more obvious.
The element composition of porous carbon materials is as shown in table 1, it can be seen that the carbon material prepared by this method contains two kinds of N and S
N content in hetero atom, C-800, C-900, C-1000 film is respectively 18.06wt%, 11.92wt% and 7.90wt%.High N
Content may hinder the crystallinity of carbon, and this is consistent to the result of tem observation with us.With the increase of carburizing temperature, N contains
Amount is reduced, but C-1000 but has more excellent degree of graphitization compared to other two samples.The variation tendency and N of S contents
Content is consistent.The result at a high temperature of certain it is meant that can promote carbon material graphitization, so as to form more orderly hole
Pattern.
The element composition of carbon material is prepared under the different carburizing temperatures of table 1.
| Element term | C | N | O | S |
| C-800 | 73.58 | 18.06 | 5.19 | 2.42 |
| C-900 | 81.16 | 11.92 | 3.86 | 2.64 |
| C-1000 | 85.90 | 7.90 | 4.12 | 1.72 |
3rd, XRD curves
Fig. 3 is the material X-ray diffraction spectrum for preparing under different carburizing temperatures.Can clearly it be seen from Fig. 3, in 2 θ=25 °
With 44 ° at respectively occur two peaks, by the reference to XRD standard spectrograms, learn they be standard carbon material peak, i.e. graphite
（002）Face and（101）Face.The two peaks can presentation materials degree of graphitization, it can be seen that C-1000 two peaks all compared with
By force, illustrate that its degree of graphitization is best.Secondly, there is peak at 2 θ=44 °, it is layer structure to illustrate material internal；But it is due to peak
It is weaker, the codope of nitrogen, sulphur is added, it is based on agraphitic carbon to show material.
3rd, electrochemical catalysis performance of N, S the codope graphitized carbon material in HER and OER
Electro-chemical test is in CHI600E electrochemical workstations（Morning is magnificent）On, chemical property is carried out using standard three electrode system
Test.Platinum filament and calomel（In saturation KCl solution）Electrode is respectively as to electrode and reference electrode, and being dripped on working electrode has
0.54 mg/cm2Porous carbon materials（Obtained according to the significant surface integrating of glass-carbon electrode）.Pass through linear sweep voltammetry（LSV）Skill
H of the art in 0.5 M2SO4（PH=0）And 1.0 M KOH（pH=14）It is bent with 5 mV/s scan rate measurement polarization in solution
Line, to study the Hydrogen evolving reaction of prepared porous carbon materials（HER）And oxygen evolution reaction（OER）Activity.Gained current potential passes through E
（Vs RHE, with respect to reversible hydrogen electrode）= E（Relative to calomel electrode）+ 0.24V+0.0591pH are corrected.The electricity of material
Chemical cycle stability is tested by chronoamperometry under constant overpotential.
Fig. 4 is the linear scan curve of material prepared by different presomas are carbonized（HER）,（1）20% Pt/C,（2）C-
1000,（3）C-900,（4）C-800,（5）Poly ion liquid PCMVImTf2N（1000 DEG C of carbonizations）,（6）Bovine serum albumin(BSA)
（BSA, 1000 DEG C of carbonizations）,（7）BSA/PCMVImTf2N（The PCMVImTf of BSA and 1000 DEG C of carbonization of 1000 DEG C of carbonizations2N is with matter
Amount compares 1:7 mixing）.As can be seen that the excellent of catalyst activity is mainly manifested in terms of two from HER curves：One is catalysis
The increase of hydrogen reduction current density, two be to be catalyzed shuffling for hydrogen reduction take-off potential.It can thus be seen that the C-1000 materials prepared
The performance of excellent liberation of hydrogen is shown, this explanation BSA doping can be improved in terms of dynamics and thermodynamics two simultaneously urges
The catalytic activity of agent.Shown according to existing research, carbon support is to influence catalyst hydrogen also containing appropriate N element
One key factor of former activity, this is also a reason of C-1000 excellent performances.C-1000 is in 10 mA/cm2Electric current it is close
Degree is lower active with very high HER, i.e., its overpotential is 165 mV, the nonmetal doping carbon nanometer that this value has substantially less than been reported
Catalyst.In addition, the result is suitable with the result of many precious metal dopings or more preferable even than them.
Fig. 5 is C-1000 materials OER in 1 M KOH solutions scanning linearity curve（HER）.As can be seen that in electric current
Density is 10 mA/cm2When, its overpotential is 460mV, and this value is better than the result of other carbon mix catalyst.C-1000 materials
Very high catalytic activity is all shown in HER and OER, this is probably because the material has higher electric conductivity, simultaneously
Its micropore and meso-hole structure provide substantial amounts of reacting environment for catalytic reaction.In addition, the synergy after nitrogen and sulphur codope
It is the basic place that the material has high catalytic activity.
Fig. 6 is C-1000 OER linear scans curves in different electrolyte.It can be seen that the material in 0.1 M KOH and
0.5 M H2SO4In overpotential be respectively 460 mV and 490 mV, show that the carbon material is separated out under condition of different pH to oxygen anti-
There should be preferable catalytic activity.
In summary, it is of the invention by bovine serum albumin（BSA）It is dissolved in poly ion liquid in DMF,
The compound presoma prepared obtains the membrane material with porous height ionomer, the membrane material through AMMONIA TREATMENT deprotonation
Further carbonization can be prepared by the material BSA PCMVImTf with excellent electro catalytic activity to material2N --- N, S codope graphitization
Carbon material.Electro-chemical test shows that the carbon material shows excellent catalytic performance in HER and OER, and it is in 10 mA/
cm2Current density under overpotential be respectively 165 mV and 460 mV, the value is higher than the non-metal catalyst reported at present.Cause
This, catalytic activity of the carbon material in HER and OER can be effectively improved by Heteroatom doping, be novel high-performance HER and
Prepared by the design of OER catalyst provides new method and thinking.
Brief description of the drawings
Fig. 1 is C-1000 SEM（SEM）Image.
Fig. 2 is BSA@PCMVImTf under different temperatures2High resolution transmission electron microscopy after N carbonizations（HRTEM）.
Fig. 3 is the BSA@PCMVImTf that prepare under different carburizing temperatures2The XRD curves of N materials.
Fig. 4 is the linear scan curve of different carbon materials（HER）,（a）20% Pt/C,（b）C-1000、（c）C-900、
（d）C-800、（e）Poly ion liquid PCMVImTf2N（1000 DEG C of carbonizations）、（f）Bovine serum albumin(BSA)（BSA, 1000 DEG C of carbonizations）、
（g）BSA/PCMVImTf2N（The PCMVImTf of BSA and 1000 DEG C of carbonization of 1000 DEG C of carbonizations2N is with mass ratio 1:7 mixing）.
Scanning linearity curves of Pt/C, C-900 and the C-1000 that Fig. 5 is 20% in 1 M KOH solutions（HER）.
Fig. 6 is linear scan curves of the C-1000 in different electrolyte solutions（OER）.
Embodiment
Below by specific embodiment to N of the present invention, the preparation of S codope graphitized carbon materials and electro catalytic activity do into
One step explanation.
Material and reagent：1- vinyl imidazoles（Pacify resistance to Jilin Chemical, 98%）, Pt/C (Alfa Aesar, Pt content 20%),
Azodiisobutyronitrile（AIBN, the triumphant letter chemistry in Tianjin, 98%）, bromoacetonitrile（Pacify resistance to Jilin Chemical, 97%）, dimethyl sulfoxide (DMSO)
（DMSO, Beijing Chemical Plant is analyzed pure）, DMF（DMF, Li Anlongbohua（Tianjin）The limited public affairs of medical chemistry
Department, analyzes pure）, methanol（Li Anlongbohua（Tianjin）Medical chemistry Co., Ltd, analyzes pure）, tetrahydrofuran（Li Anlongbohua
（Tianjin）Medical chemistry Co., Ltd, analyzes pure）, ammoniacal liquor（Yingyang City the Yellow River chemical reagent factory, analyzes pure）, absolute ethyl alcohol（Peace
Specialization, is analyzed pure）, absolute ether（Beijing Chemical Plant, is analyzed pure）, it is double（Trifyl）Acid imide lithium salts
（LiTFSI）, bovine serum albumin(BSA) V（BSA, pacifies resistance to Jilin Chemical, 98%）, mentioned reagent directly uses.
Embodiment 1
（1）The preparation of CMVImBr monomers：By 1- vinyl imidazoles（9.411 g）And bromoacetonitrile（11.995 g, mol ratio 1:1）
It is added in 50 ml round-bottomed flasks, stirs 4 ~ 5 hours at room temperature, generates the solid of yellow；By solid dissolving in methyl alcohol, then
This solution is settled in absolute ether, white solid, as 30 DEG C of oven dryings, CMVImBr monomers is finally filtrated to get；
（2）Poly ion liquid PCMVImBr preparation：By CMVImBr monomers（10 g）And AIBN（0.2 g）Initiator adds together
Enter into 250 ml round-bottomed flask, add 100 ml dimethyl sulfoxide (DMSO)s as solvent, reaction vessel is placed in ice after dissolving
In bath, logical nitrogen is vacuumized to whole reaction system, is repeated 3 times.After the solution in round-bottomed flask reaches room temperature, placed
Reacted 72 hours in 75 DEG C of oil bath.Polymerization is finished settles above-mentioned solution in tetrahydrofuran, by solid after centrifugal treating
Material is placed on 65 DEG C of drying of baking oven, obtains solid powder, as poly ion liquid PCMVImBr；
（3）Polycondensation monomer 1- cyano methyl -3- vinyl imidazoles are double（Trifyl）Acid imide（PCMVImTf2N）Preparation：
Weigh 5.52 g poly ion liquid PCMVImBr, plus 552ml distilled water, be configured to 10 g/L solution；Again by double fluoroforms
Alkane sulfimide lithium（LiTFSI）8.53 g are weighed, 170.53ml distilled water is added, is configured to 50g/L solution；Then will
Double trifluoromethanesulfonimide lithiums（LiTFSI）Solution be added dropwise to before poly ion liquid in, persistently stir 2 ~ 3 hours,
Reaction is centrifuged after terminating, gained solid distillation water washing, is dried, is obtained light tan solid powder, as poly ion liquid
PCMVImTf2N --- poly- [1- cyano methyl -3- vinyl imidazoles are double（Trifyl）Acid imide]；
（4）BSA@PCMVImTf2The preparation of N composite membranes：By PCMVImTf2N（1.1272 g）And BSA（0.1624 g, quality
Than for 7:1）It is dissolved in DMF (7 mL), obtains transparent uniform solution.The solution is applied on the glass sheet, and in 75 DEG C of baking oven
The middle h of drying 3, then sheet glass is immersed in the alcohol solution dipping 2 hours of 0.5wt% ammonia, produce BSA@PCMVImTf2N is porous
Precursor film material；
（5）BSA@PCMVImTf2The preparation of N porous carbons
The porous precursor film of above-mentioned preparation is put into tube furnace 1000 DEG C and holding 1 are warming up to 10 DEG C/min speed
Hour, room temperature is then naturally cooling to, BSA@PCMVImTf are produced2N porous carbon materials, are designated as C-1000.The carbon material is 0.5
M H2SO4And in 1M KOH solutions, its overpotential is respectively 165 mV（10 mA cm-1）With 460 mV（10 mA cm-1）.
Embodiment 2
（1）The preparation of CMVImBr monomers：Be the same as Example 1；
（2）Poly ion liquid PCMVImBr preparation：Be the same as Example 1；
（3）Polycondensation monomer 1- cyano methyl -3- vinyl imidazoles are double（Trifyl）Acid imide（PCMVImTf2N）Preparation：
Be the same as Example 1；
（4）BSA@PCMVImTf2The preparation of N composite membranes：（4）BSA@PCMVImTf2The preparation of N composite membranes：By PCMVImTf2N
（0.1624 g）And BSA（0.1624 g, mass ratio is 1:1）It is dissolved in DMF (7 mL), obtains transparent uniform solution.This is molten
Liquid is applied on the glass sheet, and dries in 75 DEG C of baking oven 3 h, then sheet glass is immersed in the alcohol solution dipping of 0.5wt% ammonia
2 hours, produce BSA@PCMVImTf2The porous precursor film materials of N；
（5）BSA@PCMVImTf2The preparation of N porous carbons：The porous precursor film of above-mentioned preparation is put into tube furnace with 10
DEG C/min speed is warming up to 1000 DEG C, and kept for 1 hour, room temperature is then naturally cooling to, BSA@PCMVImTf are produced2N is more
Hole carbon material, is designated as C-1000（1:1）.The carbon material is in 0.5 M H2SO4And in 1M KOH solutions, its overpotential is respectively 456
mV（10 mA cm-1）With 750 mV（10 mA cm-1）.
Embodiment 3
（1）The preparation of CMVImBr monomers：Be the same as Example 1；
（2）Poly ion liquid PCMVImBr preparation：Be the same as Example 1；
（3）Polycondensation monomer 1- cyano methyl -3- vinyl imidazoles are double（Trifyl）Acid imide（PCMVImTf2N）Preparation：
Be the same as Example 1；
（4）BSA@PCMVImTf2The preparation of N composite membranes：By PCMVImTf2N（1.7864 g）And BSA（0.1624g, mass ratio
For 11:1）It is dissolved in DMF (7 mL), obtains transparent uniform solution.The solution is applied on the glass sheet, and in 75 DEG C of baking oven
3 h are dried, then sheet glass is immersed in the alcohol solution dipping 2 hours of 0.5wt% ammonia, BSA@PCMVImTf are produced2Before N is porous
Drive body membrane material；
（5）BSA@PCMVImTf2The preparation of N porous carbons：By the porous precursor film of above-mentioned preparation be put into tube furnace with 10 DEG C/
Min speed is warming up to 1000 DEG C, and is kept for 1 hour, is then naturally cooling to room temperature, produces BSA@PCMVImTf2N porous carbons
Material, is designated as C-1000（11:1）.The carbon material is in 0.5 M H2SO4And in 1M KOH solutions, its overpotential is respectively 390 mV
（10 mA cm-1）With 586 mV（10 mA cm-1）.
Embodiment 4
（1）The preparation of CMVImBr monomers：Be the same as Example 1；
（2）Poly ion liquid PCMVImBr preparation：Be the same as Example 1；
（3）Polycondensation monomer 1- cyano methyl -3- vinyl imidazoles are double（Trifyl）Acid imide（PCMVImTf2N）Preparation：
Be the same as Example 1；
（4）BSA@PCMVImTf2The preparation of N composite membranes：By PCMVImTf2N（1.2992 g）And BSA（0.1624g, mass ratio
For 8:1）It is dissolved in DMF (7 mL), obtains transparent uniform solution.The solution is applied on the glass sheet, and in 75 DEG C of baking oven
3 h are dried, then sheet glass is immersed in the alcohol solution dipping 2 hours of 0.5wt% ammonia, BSA@PCMVImTf are produced2Before N is porous
Drive body membrane material；
（5）BSA@PCMVImTf2The preparation of N porous carbons：By the porous precursor film of above-mentioned preparation be put into tube furnace with 10 DEG C/
Min speed is warming up to 1000 DEG C, and is kept for 1 hour, is then naturally cooling to room temperature, produces BSA@PCMVImTf2N porous carbons
Material, is designated as C-1000（8:1）.The carbon material is in 0.5 M H2SO4And in 1M KOH solutions, its overpotential is respectively 278 mV
（10 mA cm-1）With 557 mV（10 mA cm-1）.
Embodiment 5
（1）The preparation of CMVImBr monomers：Be the same as Example 1；
（2）Poly ion liquid PCMVImBr preparation：Be the same as Example 1；
（3）Polycondensation monomer 1- cyano methyl -3- vinyl imidazoles are double（Trifyl）Acid imide（PCMVImTf2N）Preparation：
Be the same as Example 1；
（4）BSA@PCMVImTf2The preparation of N composite membranes：By PCMVImTf2N（0.812 g）And BSA（0.1624g, mass ratio
For 5:1）It is dissolved in DMF (7 mL), obtains transparent uniform solution.The solution is applied on the glass sheet, and in 75 DEG C of baking oven
3 h are dried, then sheet glass is immersed in the alcohol solution dipping 2 hours of 0.5wt% ammonia, BSA@PCMVImTf are produced2Before N is porous
Drive body membrane material；
（5）BSA@PCMVImTf2The preparation of N porous carbons：By the porous precursor film of above-mentioned preparation be put into tube furnace with 10 DEG C/
Min speed is warming up to 1000 DEG C, and is kept for 1 hour, is then naturally cooling to room temperature, produces BSA@PCMVImTf2N porous carbons
Material, is designated as C-1000（5:1）.The carbon material is in 0.5 M H2SO4And in 1M KOH solutions, its overpotential is respectively 215 mV
（10 mA cm-1）With 535 mV（10 mA cm-1）.
Claims (5)
1. the preparation method of a kind of N, S codope graphitized carbon material, is by poly ion liquid PCMVImTf2N and bovine serum albumin
BSA is dissolved in DMF, obtains the transparent uniform solution that total concentration is 46 ~ 278 g/L；Again by solution coating on the glass sheet, do
The ethanol solution of 0.4 ~ 0.5wt% ammonia is immersed in after dry 2 ~ 3 hours, obtains BSA@PCMVImTf2The porous precursor films of N；Then will
BSA@PCMVImTf2The porous precursor films of N are put into tube furnace, are warming up to 800 ~ 1000 DEG C, reach and kept after target temperature 1 ~
1.5 hours；Room temperature is naturally cooling to, N, S codope graphitized carbon materials is produced.
2. a kind of N as claimed in claim 1, the preparation method of S codope graphitized carbon materials, it is characterised in that：PCMVImTf2N
Mass ratio with bovine serum albumin BSA is 1:1~11:1.
3. a kind of N as claimed in claim 1, the preparation method of S codope graphitized carbon materials, it is characterised in that：Step（4）
In, the heating rate of tube furnace is 10 DEG C/min.
4. N prepared by method as claimed in claim 1, S codopes graphitized carbon material is applied to analysis as electrochemical catalyst
In hydrogen reaction.
5. N prepared by method as claimed in claim 1, S codopes graphitized carbon material is applied to analysis as electrochemical catalyst
In oxygen reaction.
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| CN107999109A (en) * | 2017-12-25 | 2018-05-08 | 西北师范大学 | The preparation and application of a kind of nitrogen, sulphur, phosphor codoping carbon material |
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| CN107999109A (en) * | 2017-12-25 | 2018-05-08 | 西北师范大学 | The preparation and application of a kind of nitrogen, sulphur, phosphor codoping carbon material |
| CN107999109B (en) * | 2017-12-25 | 2020-07-07 | 西北师范大学 | Preparation and application of nitrogen, sulfur and phosphorus co-doped carbon material |
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| CN109402664B (en) * | 2018-12-12 | 2020-09-29 | 浙江理工大学 | Preparation and application of graphene/polyion liquid-based carbon material |
| CN109402664A (en) * | 2018-12-12 | 2019-03-01 | 浙江理工大学 | A kind of preparation and application of graphene/poly ion liquid base carbon material |
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| CN113233461B (en) * | 2021-07-07 | 2023-02-21 | 河北省科学院能源研究所 | Preparation of non-metal biomass-based porous carbon material and hydrogen production application thereof |
| CN116063601A (en) * | 2021-10-29 | 2023-05-05 | 天目湖先进储能技术研究院有限公司 | Water-soluble polyion liquid and application thereof in lithium-sulfur battery |
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