CN107999113A - N doping porous carbon membranes with high catalytic activity and its preparation method and application - Google Patents
N doping porous carbon membranes with high catalytic activity and its preparation method and application Download PDFInfo
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- CN107999113A CN107999113A CN201711370302.8A CN201711370302A CN107999113A CN 107999113 A CN107999113 A CN 107999113A CN 201711370302 A CN201711370302 A CN 201711370302A CN 107999113 A CN107999113 A CN 107999113A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 53
- 239000012528 membrane Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 27
- 229920000642 polymer Polymers 0.000 claims abstract description 20
- 239000002131 composite material Substances 0.000 claims abstract description 15
- 229920000831 ionic polymer Polymers 0.000 claims abstract description 15
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 13
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 13
- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 13
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 12
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 238000003763 carbonization Methods 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims description 18
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000002608 ionic liquid Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- 229910021389 graphene Inorganic materials 0.000 claims description 6
- 238000012360 testing method Methods 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 5
- 150000001450 anions Chemical class 0.000 claims description 4
- -1 dimethyl methyl Chemical group 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 3
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910015898 BF4 Inorganic materials 0.000 claims description 2
- CVTZKFWZDBJAHE-UHFFFAOYSA-N [N].N Chemical compound [N].N CVTZKFWZDBJAHE-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 229910001914 chlorine tetroxide Inorganic materials 0.000 claims description 2
- 238000009826 distribution Methods 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 30
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000908 ammonium hydroxide Substances 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 abstract description 2
- 239000007772 electrode material Substances 0.000 abstract 1
- 239000011344 liquid material Substances 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- 239000005518 polymer electrolyte Substances 0.000 abstract 1
- 229920006254 polymer film Polymers 0.000 abstract 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 10
- 229920002554 vinyl polymer Polymers 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 5
- RAXXELZNTBOGNW-UHFFFAOYSA-N 1H-imidazole Chemical compound C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 206010013786 Dry skin Diseases 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- VWUCIBOKNZGWLX-UHFFFAOYSA-N 1h-imidazol-1-ium;bromide Chemical compound [Br-].C1=C[NH+]=CN1 VWUCIBOKNZGWLX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229940006460 bromide ion Drugs 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- KZMAWJRXKGLWGS-UHFFFAOYSA-N 2-chloro-n-[4-(4-methoxyphenyl)-1,3-thiazol-2-yl]-n-(3-methoxypropyl)acetamide Chemical compound S1C(N(C(=O)CCl)CCCOC)=NC(C=2C=CC(OC)=CC=2)=C1 KZMAWJRXKGLWGS-UHFFFAOYSA-N 0.000 description 1
- MLMGJTAJUDSUKA-UHFFFAOYSA-N 2-ethenyl-1h-imidazole Chemical class C=CC1=NC=CN1 MLMGJTAJUDSUKA-UHFFFAOYSA-N 0.000 description 1
- 238000009620 Haber process Methods 0.000 description 1
- 241001282153 Scopelogadus mizolepis Species 0.000 description 1
- RMLHVYNAGVXKKC-UHFFFAOYSA-N [SH2]=N.C(F)(F)F Chemical compound [SH2]=N.C(F)(F)F RMLHVYNAGVXKKC-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010959 commercial synthesis reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
- B01J35/59—Membranes
-
- 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
-
- 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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
- C25B11/031—Porous electrodes
-
- 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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/042—Electrodes formed of a single material
- C25B11/043—Carbon, e.g. diamond or graphene
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention belongs to new energy materials field, is specially a kind of N doping porous carbon membranes with high catalytic activity and its preparation method and application.The present invention synthesizes poly ion liquid material first, itself and polyacrylic acid, the mixed solution of carbon nanotubes then are made polymer film.Soak to obtain the porous composite polymer electrolyte membrane of height ion hinge by ammonium hydroxide again.This composite membrane of polymer is through carbonization treatment, you can porous N doping carbon film is made.The carbon film of preparation has controllable thickness, aperture, programmable shape, easily extensive to prepare.Nitrogen efficient stable in air can be converted into ammonia, every square metre of carbon film can prepare 0.09 gram of ammonia per hour by N doping porous carbon membranes prepared by the present invention by electro-catalysis on a large scale as the electrode material of self-supporting.Porous N doping carbon film prepared by the present invention has wide actual application prospect in energy conversion field.
Description
Technical field
The invention belongs to novel energy resource material technology field, be specially it is a kind of can self-supporting N doping porous carbon membranes and its system
Preparation Method and application.
Background technology
Ammonia (NH3) no matter as agricultural fertilizer, new energy carrier, all it act as in human society one quite heavy
The role [1-4] wanted, is chemical raw material indispensable among people's life.Only in global NH in 20153Total output is very
To having had reached 1.46 hundred million tons [1].Nitrogen (N2It is commercial synthesis NH3Primary raw material, although N in air2Content be up to
78%, but due to N2N ≡ N have high bond energy (940.95kJ mol in molecule-1) and lack permanent dipole moment, its
Exceptional stability under normal temperature and pressure.Therefore industrial utilization N2Prepare NH3Method it is very harsh.At present, aber process (Haber
Process) it is industrial production NH3Main method, its process is N2With H2High temperature and pressure (400-500 DEG C, 200-250 air
Pressure) under the action of generate ammonia.Aber process prepares NH3Annual required energy total value accounts for the 1%- of the worldwide energy gross output value
3% [4].In addition, prepare NH using aber process3During, H2Production be even more need the substantial amounts of fossil fuel (CH that burns4+
2H2O→4H2+CO2), give off substantial amounts of greenhouse gases CO2, seriously pollute environment.
The demand of grain is also increased increasingly as world population increases, along with industrial development and military compels to be essential
Will, make artificial fixed nitrogen in the beginning of this century into global great research topic.It is either cost-effective, or environmental protection,
If can be by the N in air2The ammonia of high added value is converted at normal temperatures and pressures, then this has optimization China's energy resource structure
Great strategic importance, while will also produce huge economic benefit.
Electro-catalysis technology has the advantages that efficient, easy to operate, easy realize automates [5-6], and water is a kind of source
Extensively, environmental-friendly green solvent, therefore electro-catalysis conversion N in aqueous2With very strong actual application prospect.Realize big
Scale N2The core technology of electro-catalysis Transformation Application is that research and development are efficient, stablizes the elctro-catalyst that can be mass-produced.
Since the carbon material of Heteroatom doping is cheap and easy to get, there is unique inoxidizability, high specific surface area, controllable
Electro-chemical activity and high stability under acid-base condition, it has very huge development prospect in electrochemical catalysis field
[7-10], but the carbon of Heteroatom doping is as N2At home and abroad there is presently no document report for the new material of reduction.
The content of the invention
The shortcomings that the present invention seeks to for current industrial preparative method, such as：Harsh reaction condition (high temperature and pressure),
Substantial amounts of greenhouse gases are given off, and the problems such as huge energy consumption, there is provided a kind of system cheap and easy to get, easily extensive
Porous N doping carbon film standby, that there is high electro catalytic activity and stability and its application in nitrogen fixation.The carbon film can
At normal temperatures and pressures, nitrogen efficiently is converted into ammonia in aqueous solution, prepares ammonia to be environmental-friendly, low energy consumption and provide
A kind of technical support.
One of the raw material provided by the invention for preparing N doping porous carbon membranes poly ion liquid is the ion containing nitrogen-atoms
Polymer, it is with following structure：
Wherein R is the alkyl chain or CH that carbon number is 1~142CN.X is Cl, Br, I, BF4、PF6、ClO4、CF3COO、
CF3SO3、(CF3SO2)2N、AlCl4、EtSO4、MeSO4、H2PO4、HSO4、Al2O7、N(CN)2、CH3COO、B(CN)4、BF3CF3Or
SCN。
The two of the raw material provided by the invention for preparing N doping porous carbon membranes are polyacrylic acid, it has with lower structure：
The molecular weight of polyacrylic acid is 1800~1250000KDa.
The preparation method of N doping porous carbon membranes provided by the invention, includes following four step：
(1) by above-mentioned poly ion liquid and polyacrylic acid according to 1：1~1:3 mixed in molar ratio, adds 10~500mL's
Dimethylformamide or dimethyl sulfoxide (DMSO), dissolve by heating under the conditions of 25 DEG C to 70 DEG C.Then by the carbon nanometer of 0.1~10g amounts
Pipe either graphene oxide or carbon black ultrasonic disperse in above-mentioned polymer solution.
(2) polymer solution prepared by step (1) is toppled on a glass, it is small in 25 DEG C~120 DEG C heating 2~48
When, dry out solvent.
(3) composite membrane of polymer prepared by step (2) soaks to 1 in the ammonia spirit of 0.1wt%~28wt%~
10 it is small when, apertured polymeric film can be obtained.
(4) by the apertured polymeric film prepared by step (3) in an inert atmosphere, at 300~1200 DEG C, 1.5Torr~
Under conditions of normal pressure, when carbonization 1~10 is small, porous nitrogen-doped carbon film can be obtained.
Raw material of the present invention is cheap and easy to get, and preparation method is simple, is easy to industrialized production.The N doping porous carbon membranes are in room temperature
With very high electrical conductivity, its room-temperature conductivity is up to 134S cm-1。
The thickness of the N doping porous carbon membranes is 20nm to 10cm.And with the hierarchical porous structure of gradient distribution.
The preparation method of the poly ion liquid is：
Halogenated compound prepares ionic liquid monomer with vinyl imidazole in 0 DEG C~60 DEG C reactions；Then by activity certainly
The poly ion liquid that anion is halogen is prepared by base polymerization；Then using methanol, ethanol, acetone, acetonitrile or water to be molten
Agent, adds the corresponding inorganic salts of equimolar amounts, when 0~70 DEG C of reaction 12~72 is small, obtains the corresponding target polyion of anion
Liquid.
Invention also provides N doping porous carbon membranes as application of the electrode in electro-catalysis field；
Such as using N doping porous carbon membranes as application of electrode in N2Reduction, specific practice are：By prepared porous nitrogen
For doped carbon film directly as working electrode, Ag/AgCl is reference electrode, and platinum filament is that aqueous hydrochloric acid solution is electrolyte to electrode, its
The faradic efficiency of electro-catalysis reduction ammonia is 6%, and it with very high stability, when follow-on test 192 is small, it can
Nitrogen is converted into ammonia with lasting, yield can prepare 86.4g ammonias every month for every square metre of carbon film.
The advantages and positive effects of the present invention：
Carbon film prepared by the present invention has very high electrical conductivity in room temperature, its room-temperature conductivity is up to 134S cm-1, also,
The carbon film have from macropore to it is mesoporous again to micropore hierarchical porous structure in catalytic reaction, macropore can be used as reaction substrate it is fast
Speed enters the passage of carbon film, and mesoporous and micropore then provides big specific surface area and catalytic reaction activity site, can significantly improve
Reaction efficiency；
Compared to the method (high temperature and pressure, and giving off during ammonia is produced a large amount of of more current industrial production ammonia
GHG carbon dioxide, seriously pollute environment, energy expenditure is very big), raw material of the present invention is cheap and easy to get, preparation method letter
It is single, it is easily extensive to prepare.Porous carbon membranes prepared by this method are in normal temperature and pressure, aqueous solution by electrocatalytic reaction by nitrogen
Efficient to be converted into ammonia, every square metre of carbon film can produce 0.09g ammonias per hour, and long term stability tests are found, continuously
Test 8 days, its performance has no reduction.Ammonia production process is environmental-friendly, and low energy consumption, is easy to industrialized production, is expected to extensive
Using.
Brief description of the drawings
Fig. 1 is the flow chart for preparing porous N doping carbon film；
Fig. 2 is the nuclear magnetic spectrogram of polyvinyl imidazol trifluoro methylsulfonimide ionic liquid；
Fig. 3 is carbon nanotubes number dispersed in the dimethyl formamide solution of poly ion liquid/polyacrylic acid
Photo；
Fig. 4 is the photo and stereoscan photograph of poly ion liquid/polyacrylic acid/carbon nanotubes；
Fig. 5 is the photo and stereoscan photograph of porous N doping carbon film；
Fig. 6 is the performance test results that nitrogen electro-catalysis is converted into ammonia, and (A) is faraday's effect of ammonia under different voltages
Rate, the yield of ammonia under (B) different voltages, (C) prepares the stabilization of ammonia under -0.1 volt (with respect to hydrogen electrode potential)
Property test.
Embodiment
Below by some embodiments, exemplary explanation and help further understand the present invention.
Embodiment 1：
(1) poly ion liquid is prepared：
In the round-bottomed flask of 250mL, 9.4g vinyl imidazoles, 12g bromoacetonitriles are dissolved in the ethanol solution of 100mL, 40 DEG C
React 24 it is small when, the vinyl iminazole ionic liquid monomer of grey, yield can be obtained:95%.Take the vinyl miaow of above-mentioned preparation
Oxazolinium ion liquid monomer 10g, is dissolved in dimethylformamide, adds 0.2g azodiisobutyronitriles, and 70 DEG C of reactions 48 are small
When can obtain white polyvinyl imidazol bromide ion liquid.10g polyvinyl imidazol bromide ion liquid is weighed, is dissolved in
In the deionized water of 1000mL, add 13g fluoroform sulfimide lithiums, be stirred at room temperature 4 it is small when, target poly ion liquid can be obtained,
Polyvinyl imidazol trifluoro methylsulfonimide ionic liquid.
(2) polymer/carbon nano-tube composite membrane is prepared：
By the polyvinyl imidazol trifluoro methylsulfonimide ionic liquid of the above-mentioned preparations of 1g, 0.18g molecular weight is 100,
The polyacrylic acid and 0.1g carbon nanotubes ultrasonic dissolutions of 000KDa, is dispersed in the dimethylformamide of 10mL, then by it
Topple on a glass, when 80 DEG C of dryings 5 are small.Then, immerse 0.1% ammonia spirit, place 2 it is small when, can obtain polymer/
Carbon nano-tube compound film.
(3) N doping porous carbon membranes are prepared：Under nitrogen protection, 900 DEG C, carbonization 2 is small for polymer/carbon nano-tube composite membrane
When, porous nitrogen-doped carbon film can be obtained.
Embodiment 2：Prepare polymer/carbon nano-tube composite membrane：
(1) by 5g polyvinyl imidazol trifluoro methylsulfonimide ionic liquids, 1g molecular weight is the polyacrylic acid of 1800KDa
And 0.5g carbon nanotubes ultrasonic dissolutions, it is dispersed in the dimethylformamide of 100mL, is then poured upon on a glass,
When 80 DEG C of dryings 10 are small.Then, 1% ammonia spirit is immersed, when placement 4 is small, polymer/carbon nano-tube composite membrane can be obtained.
(2) N doping porous carbon membranes are prepared：Polymer/carbon nano-tube composite membrane under nitrogen protection, 300 DEG C, carbonization 10
Hour, porous nitrogen-doped carbon film can be obtained.
Embodiment 3：
(1) porous polymer/graphene oxide composite membrane is prepared：2g diallyl dimethyl trifluoros methylsulfonyl is sub-
Amine ammonium, 0.4g molecular weight are the polyacrylic acid and 0.5g graphene oxide ultrasonic dissolutions of 450,000KDa, are dispersed in 10mL's
In dimethyl sulfoxide (DMSO), then it is poured upon on a glass, when 90 DEG C of dryings 36 are small.Then, immerse 0.3% ammonium hydroxide it is molten
Liquid, when placement 6 is small, can obtain polymer/graphene oxide composite membrane.
(2) porous N doping carbon film is prepared：Polymer/graphene oxide composite membrane under nitrogen protection, 500 DEG C, carbonization 4
Hour, porous nitrogen-doped carbon film can be obtained.
Embodiment 4：
Prepare porous polymer/carbon black composite membrane：By 2g diallyl dimethyl trifluoro methylsulfonimide ammoniums, 0.4g
The polyacrylic acid and 1g carbon black ultrasonic dissolutions that molecular weight is 1,250,000KDa, are dispersed in the dimethyl sulfoxide (DMSO) of 50mL, so
After be poured upon on a glass, 90 DEG C it is dry 36 it is small when.Then, 1% ammonia spirit is immersed, when placement 6 is small, must can be gathered
Compound/carbon black composite membrane.
Prepare porous N doping carbon film：Polymer/carbon black composite membrane under nitrogen protection, 1200 DEG C, can when carbonization 4 is small
Obtain porous nitrogen-doped carbon film.
Embodiment 5：
Nitrogen electro-catalysis reduces：The N doping porous carbon membranes prepared using above-described embodiment 2 are used as working electrode, Ag/AgCl
As reference electrode, Pt is used as and is assembled into electrolytic cell as electrolyte to electrode, the hydrochloric acid solution of 0.1M.Nitrogen is directly logical
Enter the aqueous hydrochloric acid solution of 0.1M, by N under -0.1V (to standard hydrogen electrode potential)2It is catalytically conveted to ammonia.
Experiment test shows that the porous N doping carbon film of above-mentioned preparation converts N2Faradic efficiency be 6%, and its have
There is very high stability, follow-on test 192h, what it can continue is converted into nitrogen ammonia, and yield is every square metre of carbon film
0.09g ammonias can be prepared per hour.Compared with preparing ammonia with current industrial Hubble's method, present invention process is simple, and raw material is inexpensive
It is easy to get, the preparation of ammonia carries out at normal temperatures and pressures, and yield is high, saves the energy, is expected to be used for the preparation of extensive ammonia.
Bibliography：
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Claims (9)
- A kind of 1. preparation method of the N doping porous carbon membranes with high catalytic activity of self-supporting, it is characterised in that specific steps It is as follows：(1) by poly ion liquid and polyacrylic acid according to 1：1~1:3 mixed in molar ratio, adds the dimethyl methyl of 10~500mL Acid amides or dimethyl sulfoxide (DMSO), dissolve by heating under the conditions of 25 DEG C to 70 DEG C；Then by carbon nanotubes, graphene oxide or carbon black Ultrasonic disperse is in above-mentioned polymer solution；(2) polymer solution prepared by step (1) is toppled on a glass, when 25 DEG C~120 DEG C heating 2~48 are small, Dry out solvent；(3) it is small that the composite membrane of polymer prepared by step (2) is soaked to 1~10 in the ammonia spirit of 0.1wt%~28wt% When, obtain apertured polymeric film；(4) by the apertured polymeric film prepared by step (3) in an inert atmosphere, at 300~1200 DEG C, 1.5Torr~normal pressure Under conditions of, when carbonization 1~10 is small, cooled to room temperature, finally obtains N doping porous carbon membranes.
- 2. preparation method according to claim 1, it is characterised in that the poly ion liquid be containing nitrogen-atoms from Sub- polymer, has following structure：Wherein R is the alkyl chain or CH that carbon number is 1~142CN；X is Cl, Br, I, BF4、PF6、ClO4、CF3COO、CF3SO3、 (CF3SO2)2N、AlCl4、EtSO4、MeSO4、H2PO4、HSO4、Al2O7、N(CN)2、CH3COO、B(CN)4、BF3CF3Or SCN.
- 3. preparation method according to claim 1, it is characterised in that the polyacrylic acid has with lower structure：The molecular weight of polyacrylic acid is 1800~1250000KDa.
- 4. according to the preparation method described in claim 1,2 or 3, it is characterised in that the preparation method of the poly ion liquid It is：Halogenated compound prepares ionic liquid monomer with vinyl imidazole in 0 DEG C~60 DEG C reactions；Then living radical is passed through The poly ion liquid that anion is halogen is prepared in polymerization；Then using methanol, ethanol, acetone, acetonitrile or water as solvent, add Enter the corresponding inorganic salts of equimolar amounts, 0~70 reaction 12~72 it is small when, obtain the corresponding target poly ion liquid of anion.
- 5. according to the preparation method described in claim 1,2 or 3, it is characterised in that the N doping porous carbon membranes described in step (4) Thickness be 20nm to 10cm.
- 6. the N doping porous carbon membranes that the preparation method of a kind of claim 1,2 or 3 obtains.
- 7. N doping porous carbon membranes according to claim 6, it is characterised in that the N doping porous carbon membranes have gradient The hierarchical porous structure of distribution.
- 8. N doping porous carbon membranes described in a kind of claim 6 are as application of the electrode in electro-catalysis field.
- 9. application according to claim 8, it is characterised in that using N doping porous carbon membranes as application of electrode in N2Reduction, Specific practice is：By prepared N doping porous carbon membranes directly as working electrode, Ag/AgCl is reference electrode, and platinum filament is To electrode, aqueous hydrochloric acid solution is electrolyte；The faradic efficiency of electro-catalysis reduction ammonia is 6%, and with very high steady Qualitative, when follow-on test 192 is small, what can be continued is converted into nitrogen ammonia, and yield every month can for every square metre of carbon film Prepare 86.4g ammonias.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108745399A (en) * | 2018-05-28 | 2018-11-06 | 南开大学 | Heteroatom doping porous carbon membranes and its preparation method and application |
| CN114471608A (en) * | 2020-10-26 | 2022-05-13 | 中国石油化工股份有限公司 | Method for hydrofining and purifying diethylene glycol |
| CN114481189A (en) * | 2022-01-24 | 2022-05-13 | 中国科学院合肥物质科学研究院 | CCM membrane electrode, preparation method thereof and application thereof in preparing ammonia by electrocatalysis of nitrate reduction |
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| CN105845453A (en) * | 2016-05-26 | 2016-08-10 | 西北师范大学 | Nitrogen-doped porous structure carbon material based on polyion liquid and preparation method thereof |
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| CN105845453A (en) * | 2016-05-26 | 2016-08-10 | 西北师范大学 | Nitrogen-doped porous structure carbon material based on polyion liquid and preparation method thereof |
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| HONG WANG ET AL: "Efficient Electrocatalytic Reduction of CO2 by Nitrogen-Doped Nanoporous Carbon/Carbon Nanotube Membranes: A Step Towards the Electrochemical CO2 Refinery", 《ANGEWANDTE CHEMIE》 * |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108745399A (en) * | 2018-05-28 | 2018-11-06 | 南开大学 | Heteroatom doping porous carbon membranes and its preparation method and application |
| CN114471608A (en) * | 2020-10-26 | 2022-05-13 | 中国石油化工股份有限公司 | Method for hydrofining and purifying diethylene glycol |
| CN114471608B (en) * | 2020-10-26 | 2023-07-21 | 中国石油化工股份有限公司 | Method for refining and purifying diethylene glycol through hydrofining |
| CN114481189A (en) * | 2022-01-24 | 2022-05-13 | 中国科学院合肥物质科学研究院 | CCM membrane electrode, preparation method thereof and application thereof in preparing ammonia by electrocatalysis of nitrate reduction |
| CN114481189B (en) * | 2022-01-24 | 2023-07-18 | 中国科学院合肥物质科学研究院 | CCM membrane electrode, preparation method thereof and application thereof in preparing ammonia through electrocatalytic nitrate reduction |
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