CN109499599A - Pyridine nitrogen-enriched carbon nanotube catalyst and preparation method and application thereof - Google Patents
Pyridine nitrogen-enriched carbon nanotube catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 71
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 55
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 40
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 30
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 23
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 23
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 38
- 229910052757 nitrogen Inorganic materials 0.000 claims description 19
- 238000006555 catalytic reaction Methods 0.000 claims description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- 239000003446 ligand Substances 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 150000003233 pyrroles Chemical class 0.000 claims description 3
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 2
- 239000002109 single walled nanotube Substances 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical group C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 claims 1
- 229960004424 carbon dioxide Drugs 0.000 description 23
- 239000007864 aqueous solution Substances 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical group [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910002090 carbon oxide Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000002048 multi walled nanotube Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000011736 potassium bicarbonate Substances 0.000 description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001485 argon Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000005430 electron energy loss spectroscopy Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- 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
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Pyridine Compounds (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a pyridine nitrogen-enriched carbon nanotube catalyst, which comprises a carbon nanotube and nitrogen atoms doped in the carbon nanotube; the doping amount of the nitrogen atoms is 1-2.5 wt%, the nitrogen atoms contain pyridine nitrogen, and the pyridine nitrogen accounts for 55-80 wt% of the total amount of the nitrogen atoms. The catalyst has high pyridine nitrogen content, and when the catalyst is used for electrocatalytic reduction of carbon dioxide into carbon monoxide, the product selectivity of the carbon monoxide is high, the current density is high, and the catalyst has high stability. The invention also discloses a preparation method and application of the catalyst.
Description
Technical field
The present invention relates to electro-catalysis technical fields.More particularly, to a kind of pyridine nitrogen be enriched with carbon nano-tube catalyst and
Preparation method and application.
Background technique
Carbon dioxide is as one of the predominant gas for causing greenhouse effects, and largely discharge is so that greenhouse effects gradually add
A series of problems, such as play, brings sea-level rise therewith, desertification of land.Meanwhile carbon dioxide is a kind of carbon source abundant again,
If carbon compound can be translated into, and then fuels and chemicals are obtained, will alleviating the energy and environment simultaneously, this is two big
Major issue.Therefore, the conversion of carbon dioxide is significantly.
Noble metal based electrocatalyst such as gold, silver can be under lower overpotential, and highly selective electro-catalysis restores dioxy
Change carbon, and stability with higher.But since its content in the earth's crust is lower, in addition, price is costly, because
This, large-scale use is restricted.There is greater activity, the cheap catalyst of stability to be used for carbon dioxide also for exploitation
Original is vital.Cheap metal base catalyst such as copper, tin and cobalt etc. have been achieved for preferably being in progress.
Many reports before show that pyridine nitrogen is the chief active site of metallising radical nitrogen-doped carbon material, still
The percentage composition for the nitrogen-doped carbon pipe pyridine nitrogen that can be obtained at present is lower, so that its application is by biggish limitation.
Accordingly, it is desirable to provide a kind of new catalyst, to solve above-mentioned technical problem.
Summary of the invention
The first purpose of this invention is to provide a kind of pyridine nitrogen enrichment carbon nano-tube catalyst, which has height
Pyridine nitrogen content, when to be used for electro-catalysis reduction carbon dioxide be in carbon monoxide, the selectivity of product of carbon monoxide is high,
Current density is big, and catalyst stability with higher.
Second object of the present invention is to provide a kind of preparation method of pyridine nitrogen enrichment carbon nano-tube catalyst.
Third object of the present invention is to provide a kind of pyridine nitrogen enrichment carbon nano-tube catalyst and restores two in electro-catalysis
Carbonoxide is the application in carbon monoxide.
In order to achieve the above first purpose, the present invention provides a kind of pyridine nitrogen enrichment carbon nano-tube catalyst, the catalysis
Agent includes carbon nanotube and the nitrogen-atoms that is entrained in carbon nanotube；The doping of the nitrogen-atoms is 1-2.5wt%, the nitrogen
It include pyridine nitrogen in atom, the pyridine nitrogen accounts for the 55-80wt% of the nitrogen-atoms total amount.
In the technical solution, under conditions of above-mentioned pyridine nitrogen content, by the doping for adjusting pyridine nitrogen, thus it is possible to vary
The current density of product carbon monoxide, pyridine nitrogen content is higher, and the current density of carbon monoxide is bigger；Contained by adjusting pyridine nitrogen
Measure percentage, thus it is possible to vary the selectivity of product carbon monoxide, pyridine nitrogen content is higher, and the selectivity of product of carbon monoxide is got over
It is high.
It preferably, also include pyrroles's nitrogen and graphite nitrogen in the nitrogen-atoms.
To reach above-mentioned second purpose, the present invention provides a kind of preparation side of pyridine nitrogen enrichment carbon nano-tube catalyst
Method, this method comprises the following steps:
Carbon nanotube is dispersed in solvent, adds containing n-donor ligand, after mixing solvent evaporated, obtains presoma, and
The presoma is ground into powdery；
Powdery precursor obtained above is heat-treated, the pyridine nitrogen enrichment carbon nano-tube catalyst is obtained.
Preferably, the carbon nanotube is in single-walled carbon nanotube, multi-walled carbon nanotube and carboxylic carbon nano-tube
It is one or more of.
Preferably, the solvent is the mixed liquor of water and ethyl alcohol, wherein the volume ratio of water and ethyl alcohol is 3:1-1:3.Its
In, the dosage of solvent is advisable with that can dissolve containing n-donor ligand.
Preferably, the atmosphere used that is heat-treated is one or more of ammonia, argon gas, nitrogen.
Preferably, the condition of the heat treatment are as follows: be warming up to 300-700 DEG C in room temperature with the rate of 3-5 DEG C/min, herein
At a temperature of keep the temperature 2-4h, then room temperature is cooled to the rate of 3-5 DEG C/min.
Preferably, the containing n-donor ligand is selected from 1,10- ferrosin, 2,2- bipyridyl and 4, one of 4- bipyridyl or several
Kind；Preferably, the mass ratio of the carbon nanotube and containing n-donor ligand is 1:1-1:5.
Preferably, the grinding carries out in the agate mortar.
To reach above-mentioned third purpose, the present invention provide a kind of pyridine nitrogen enrichment carbon nano-tube catalyst electro-catalysis also
Former carbon dioxide is the application in carbon monoxide.
Above-mentioned pyridine nitrogen enrichment carbon nanotube is used for electrochemically reducing carbon dioxide in aqueous solution electrolysis liquid, one oxygen of product
Selectivity height, the current density for changing carbon are big, and catalyst stability is good.
Preferably, the electrolyte is NaHCO3、KHCO3, one of NaCl and KCl.
Preferably, the concentration of electrolyte is 0.1-1M.
Preferably, NaHCO is being used3、KHCO3When as electrolyte, in -0.6~-0.9V vs.RHE voltage range,
The selectivity of product carbon monoxide is greater than 90%.
Beneficial effects of the present invention are as follows:
1, pyridine nitrogen of the invention enrichment carbon nano-tube catalyst can be highly selective by carbon dioxide in aqueous solution
Carbon monoxide is converted to, catalytic performance is high, and current density is high, and the stability of the catalyst is good, in carbon dioxide electroreduction
There is good application prospect in field.
2, the reduction that pyridine nitrogen of the invention enrichment carbon nano-tube catalyst can be highly selective in wider potential range
Carbon dioxide is carbon monoxide.
3, the content of pyridine nitrogen in the pyridine nitrogen enrichment carbon nano-tube catalyst being prepared in preparation method of the invention
It is higher.
Detailed description of the invention
Specific embodiments of the present invention will be described in further detail with reference to the accompanying drawing.
Fig. 1 shows the X-ray diffraction curve of the catalyst of the preparation of the embodiment of the present invention 1.
Fig. 2 shows the transmission electron microscope photos of catalyst prepared by the embodiment of the present invention 1.
Fig. 3 shows the electron scanning micrograph of the catalyst of the preparation of the embodiment of the present invention 1.
Fig. 4 shows the x-ray photoelectron spectroscopy figure of the nitrogen of the catalyst of the preparation of the embodiment of the present invention 1.
Fig. 5 shows 0.5M NaHCO of the catalyst in saturation carbon dioxide and argon gas of the preparation of the embodiment of the present invention 13It is water-soluble
Linear volt-ampere curve in liquid.
Fig. 6 shows 0.5M NaHCO of the catalyst in saturation carbon dioxide of the preparation of the embodiment of the present invention 1,2,33Aqueous solution
In carbon monoxide faradic efficiency-voltage pattern.
Fig. 7 shows 0.5M NaHCO of the catalyst in saturation carbon dioxide of the preparation of the embodiment of the present invention 1,2,33Aqueous solution
In carbon monoxide Current density-voltage figure.
Fig. 8 shows 0.5M NaHCO of the catalyst in saturation carbon dioxide of the preparation of the embodiment of the present invention 13In aqueous solution
Product faradic efficiency and current density-time diagram, test voltage are -0.8V vs.RHE.
Specific embodiment
In order to illustrate more clearly of the present invention, the present invention is done further below with reference to preferred embodiments and drawings
It is bright.Similar component is indicated in attached drawing with identical appended drawing reference.It will be appreciated by those skilled in the art that institute is specific below
The content of description is illustrative and be not restrictive, and should not be limited the scope of the invention with this.
Embodiment 1
Pyridine nitrogen is enriched with the preparation method of carbon nano-tube catalyst, includes the following steps:
600mg 1-10 ferrosin and 200mg multi-walled carbon nanotube are dispersed to the mixing of 25ml ethyl alcohol and 25ml deionized water
In solution, it is stirred at room temperature 12 hours, then solvent evaporated obtains electro-catalysis after grinding in an agate mortar at 105 DEG C
The presoma of agent；Take elctro-catalyst presoma to be placed in porcelain boat, be heat-treated in tube furnace, with 5 DEG C/min from room temperature to
It 700 DEG C, is kept for 3 hours, room temperature is then cooled to 3.3 DEG C/min, heat-treating atmosphere is ammonia atmosphere, obtains the pyridine nitrogen
It is enriched with carbon nano-tube catalyst.
The X-ray diffraction curve of the catalyst that the present embodiment is prepared is as shown in Figure 1, as seen from the figure, the present embodiment system
Standby catalyst has (002), (100) and (004) three typical crystal face of carbon nanotube.
The electron scanning micrograph of catalyst manufactured in the present embodiment is as shown in Fig. 2, as seen from the figure, the present embodiment system
Standby catalyst keeps the original structure of carbon nanotube.
The scanning transmission electron microscope of catalyst manufactured in the present embodiment and electron energy loss spectroscopy (EELS) photo such as Fig. 3 institute
Show, as seen from the figure, three kinds of carbon, nitrogen and oxygen elements are evenly distributed in carbon nanotube in catalyst manufactured in the present embodiment.
The x-ray photoelectron spectroscopy of the nitrogen of catalyst manufactured in the present embodiment is as shown in figure 4, as seen from the figure, this reality
The catalyst institute Nitrogen element for applying example preparation has pyridine, pyrroles and graphite nitrogen three types, wherein based on pyridine nitrogen, pyridine
The percentage that nitrogen accounts for total nitrogen content is 61%.
The application of elctro-catalyst electro-catalysis reduction carbon dioxide in water solution system:
The performance of carbon dioxide electroreduction is tested in the H-type electrolytic cell of sealing using three-electrode system, wherein platinum filament is made
For to electrode, saturated calomel electrode is reference electrode, and the glass-carbon electrode of supported catalyst is working electrode, electric in the present embodiment
Solution liquid is 0.5M NaHCO3, saturation carbon dioxide or argon gas are passed through before test, gas-phase product carries out detection point using gas-chromatography
Analysis, liquid product are tested and analyzed using nuclear-magnetism.It is 0.05mV/s, electrolysis time 3600s that linear volt-ampere curve, which sweeps speed,.
Catalyst manufactured in the present embodiment is in saturation carbon dioxide and the 0.5M NaHCO of argon gas3Linear volt in aqueous solution
It is as shown in Figure 5 to pacify curve.As shown in Figure 5, in the case where being saturated carbon dioxide, current density increases rapidly since 0.45V vs.RHE
Greatly, and under the conditions of being saturated argon gas, electric current is not dramatically increased, illustrates that the catalyst of above-mentioned preparation has electro-catalysis reduction two
The activity of carbonoxide.
0.5M NaHCO of the catalyst manufactured in the present embodiment in saturation carbon dioxide3The oxygen being electrolysed in aqueous solution
It is as shown in Figure 6 to change carbon faradic efficiency-voltage pattern.It will be appreciated from fig. 6 that above-mentioned catalyst can be in -0.5~-1.0V vs.RHE voltage
Efficient electro-catalysis reduction carbon dioxide is carbon monoxide in range, in -0.6~-0.9V vs.RHE voltage range, carbon monoxide
Faradic efficiency maintain 95%, illustrate above-mentioned catalyst have preferable selectivity of product.
0.5M NaHCO of the catalyst manufactured in the present embodiment in saturation carbon dioxide3The oxygen being electrolysed in aqueous solution
It is as shown in Figure 7 to change carbon Current density-voltage figure.As gradually bearing for voltage is moved, the current density of carbon monoxide is gradually increased, most
High current density is 23mA/cm2。
0.5M NaHCO of the catalyst manufactured in the present embodiment in saturation carbon dioxide3Product faraday effect in aqueous solution
Rate and current density-time diagram are as shown in figure 8, test voltage is -0.8V vs.RHE.In 40 hours stability tests,
The faradic efficiency of product carbon monoxide can maintain 95% or so, and current density can maintain 15mA/cm2More than, illustrate this
The catalyst of embodiment preparation has preferable long-time stability.
Embodiment 2
Embodiment 1 is repeated, difference is, heat treatment temperature is changed to 500 DEG C by 700 DEG C, obtained elctro-catalyst pattern
Nitrogen content similar with the elctro-catalyst that embodiment 1 obtains but total is down to 2.0%, and pyridine nitrogen percentage is 58.7%.
0.5M NaHCO of the catalyst manufactured in the present embodiment in saturation carbon dioxide3The oxygen being electrolysed in aqueous solution
Change the electro-catalysis that obtained elctro-catalyst selectivity of product and embodiment 1 obtain as shown in Figure 6 of carbon faradic efficiency-voltage pattern
Agent is not much different.
0.5M NaHCO of the catalyst manufactured in the present embodiment in saturation carbon dioxide3The oxygen being electrolysed in aqueous solution
It is as shown in Figure 7 to change carbon Current density-voltage figure.The maximum current density of carbon monoxide is 13mA/cm2。
Embodiment 3
Embodiment 1 is repeated, difference is, heat treatment temperature is changed to 300 DEG C by 700 DEG C, obtained electro-catalysis dosage form
Looks are similar with the elctro-catalyst that embodiment 1 obtains, but total nitrogen content is down to 1.0%, and pyridine nitrogen percentage is 79.6%.
0.5M NaHCO of the catalyst manufactured in the present embodiment in saturation carbon dioxide3The oxygen being electrolysed in aqueous solution
It is as shown in Figure 6 to change carbon faradic efficiency-voltage.The electro-catalysis that obtained elctro-catalyst selectivity of product and embodiment 1 obtain
Agent is not much different.
0.5M NaHCO of the catalyst manufactured in the present embodiment in saturation carbon dioxide3The oxygen being electrolysed in aqueous solution
It is as shown in Figure 7 to change carbon Current density-voltage figure.The maximum current density of carbon monoxide is 8mA/cm2。
Comparative example 1
Embodiment 1 is repeated, difference is, 1-10 ferrosin is added without in precursor preparation, remaining condition is constant, obtains
The total nitrogen content of catalyst is 0.26%, and pyridine nitrogen percentage is.Electro-catalysis effect is decreased obviously, carbon monoxide maximum faraday
Efficiency is 60%, maximum current density 0.8mA/cm2。
Comparative example 2
Embodiment 1 is repeated, difference is, 1-10 ferrosin is added without in precursor preparation, and heat-treating atmosphere is argon gas gas
Atmosphere, remaining condition is constant, and nitrogen is not detected in obtained catalyst.Almost without carbon dioxide catalytic activity, a maximum oxygen
Changing carbon faradic efficiency is only 5%.The doping for illustrating nitrogen is that there is catalyst electro-catalysis to restore the active master of carbon dioxide
Want reason.
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair
The restriction of embodiments of the present invention may be used also on the basis of the above description for those of ordinary skill in the art
To make other variations or changes in different ways, all embodiments can not be exhaustive here, it is all to belong to this hair
The obvious changes or variations that bright technical solution is extended out are still in the scope of protection of the present invention.
Claims (9)
1. a kind of pyridine nitrogen is enriched with carbon nano-tube catalyst, which is characterized in that the catalyst includes carbon nanotube and is entrained in
Nitrogen-atoms in carbon nanotube；The doping of the nitrogen-atoms is 1-2.5wt%, includes pyridine nitrogen in the nitrogen-atoms, described
Pyridine nitrogen accounts for the 55-80wt% of the nitrogen-atoms total amount.
2. pyridine nitrogen according to claim 1 is enriched with carbon nano-tube catalyst, which is characterized in that also wrapped in the nitrogen-atoms
Containing pyrroles's nitrogen and graphite nitrogen.
3. such as the preparation method of the described in any item pyridine nitrogen enrichment carbon nano-tube catalysts of claim 1-2, which is characterized in that
Include the following steps:
Carbon nanotube is dispersed in solvent, adds containing n-donor ligand, after mixing solvent evaporated, obtains presoma, and should
Presoma is ground into powdery；
Powdery precursor obtained above is heat-treated, the pyridine nitrogen enrichment carbon nano-tube catalyst is obtained.
4. preparation method according to claim 3, which is characterized in that the carbon nanotube is selected from single-walled carbon nanotube, more
One or more of wall carbon nano tube and carboxylic carbon nano-tube.
5. preparation method according to claim 3, which is characterized in that the solvent is the mixed liquor of water and ethyl alcohol, wherein
The volume ratio of water and ethyl alcohol is 3:1-1:3.
6. preparation method according to claim 3, which is characterized in that it is described be heat-treated the atmosphere that uses for ammonia, argon gas,
One or more of nitrogen.
7. preparation method according to claim 3, which is characterized in that the condition of the heat treatment are as follows: in room temperature with 3-5
DEG C/rate of min is warming up to 300-700 DEG C, 2-4h is kept the temperature at this temperature, then room temperature is cooled to the rate of 3-5 DEG C/min.
8. preparation method according to claim 3, which is characterized in that the containing n-donor ligand is selected from 1,10- ferrosin, 2,2-
One or more of bipyridyl and 4,4- bipyridyl；Preferably, the mass ratio of the carbon nanotube and containing n-donor ligand is 1:1-
1:5。
9. as the described in any item pyridine nitrogen enrichment carbon nano-tube catalysts of claim 1-2 are in electro-catalysis reduction carbon dioxide
Application in carbon monoxide.
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