CN109921037A - Preparation method and application of Fe/N/C co-doped electrocatalyst for efficient oxygen reduction reaction - Google Patents
Preparation method and application of Fe/N/C co-doped electrocatalyst for efficient oxygen reduction reaction Download PDFInfo
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- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000001301 oxygen Substances 0.000 title claims abstract description 22
- 238000006722 reduction reaction Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims description 22
- 239000010411 electrocatalyst Substances 0.000 title claims 10
- 239000003054 catalyst Substances 0.000 claims abstract description 40
- 238000000197 pyrolysis Methods 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000006229 carbon black Substances 0.000 claims abstract description 20
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 12
- 239000008103 glucose Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 12
- 239000000725 suspension Substances 0.000 claims abstract description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims abstract description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims abstract 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 84
- 229920000877 Melamine resin Polymers 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 230000035484 reaction time Effects 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 7
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims 3
- 239000012467 final product Substances 0.000 claims 1
- 239000011261 inert gas Substances 0.000 claims 1
- 238000010992 reflux Methods 0.000 claims 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims 1
- 238000000967 suction filtration Methods 0.000 claims 1
- 238000009210 therapy by ultrasound Methods 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 36
- 239000000843 powder Substances 0.000 abstract description 32
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 19
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 12
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 abstract description 11
- 239000007787 solid Substances 0.000 abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 7
- 239000001257 hydrogen Substances 0.000 abstract description 7
- 230000002441 reversible effect Effects 0.000 abstract description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000003837 high-temperature calcination Methods 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- 235000019241 carbon black Nutrition 0.000 description 15
- 239000013067 intermediate product Substances 0.000 description 12
- 238000012546 transfer Methods 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 8
- 150000007974 melamines Chemical class 0.000 description 8
- 150000002823 nitrates Chemical class 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 7
- 239000000446 fuel Substances 0.000 description 7
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 6
- 238000004502 linear sweep voltammetry Methods 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000010953 base metal Substances 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 239000008236 heating water Substances 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000000739 chaotic effect Effects 0.000 description 1
- 238000000970 chrono-amperometry Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The invention belongs to electro-catalysis technical fields, and in particular to a kind of for the Fe/N/C codope method for preparing catalyst of efficient oxygen reduction reaction and its application.It, which is synthesized, mainly passes through two steps of hydro-thermal reaction and high temperature pyrolysis, the first step is that carbon black, glucose, lauryl sodium sulfate and molysite are dissolved in secondary water, by being ultrasonically formed unit for uniform suspension, then mixed solution is placed in progress hydro-thermal reaction in reaction kettle and obtains black solid powder, i.e. presoma；In second step, presoma is sufficiently mixed according to a certain percentage with nitrogen source, high-temperature calcination in a nitrogen atmosphere obtains Fe/N/C codope catalyst.Prepared catalyst can see apparent active particle and more uniformly be doped in carbon skeleton, related Electrochemical results show that the catalyst can be with the oxygen reduction reaction (ORR) in efficient catalytic alkaline medium, half wave potential reaches 821 mV(relative to reversible hydrogen electrode) it is slightly below the 857mV of business Pt/C, while there is the stability and methanol tolerance performance better than the latter.
Description
Technical field
The invention belongs to electro-catalysis technical fields, and in particular to a kind of Fe/N/C codope for efficient oxygen reduction reaction
Method for preparing catalyst and its application.
Background technique
Fuel cell as a kind of new green energy resource mode, due to its have the characteristics that efficiently, it is environmentally friendly increasingly by
The common concern of people.Occur in the oxygen reduction process (ORR) of fuel battery negative pole to be a highly important half-reaction, but
Its kinetics slowly significantly limits the efficiency of fuel cell.Currently, platinum and its alloy catalyst are considered as performance
Optimal ORR catalyst, but the factors such as it is expensive, reserves are low the large-scale commercial application of fuel cell is caused it is huge
Big limitation.Therefore, the novel cheap non-precious metal catalyst with excellent properties is designed and developed to replace platinum based catalyst
Just seem very it is necessary to.
The base metals such as Fe, Co, Ni and its compound rich reserves in nature, it is cheap and be easy to get, in recent years
Research shows that non-precious metal catalyst shows the excellent ORR performance for the noble metal that can match in excellence or beauty, become building ORR fuel cell yin
The important component of electrode catalyst.Wherein, one or more heterogeneous element (N, S, B, P are introduced in non-precious metal catalyst
Deng) its catalytic activity and stability can be effectively promoted, being substantially improved for performance may be from their unique electronics knots
Structure and the more active sites being exposed by regulating and controlling pattern, make it easier to the reduction of catalytic oxygen, reduce reaction energy
It builds.Since carbon nanomaterial (carbon black, carbon nanotube, carbon nano-fiber, graphene and nano-porous structure carbon etc.) is with excellent
Electric conductivity and big specific surface area, therefore suitable carbon material would generally be added during the preparation process as skeleton and conductive base
Bottom.But the preparation methods of most of reports are complex, and it is simple and have excellent performance to develop a kind of preparation process in this context
Base metal ORR catalyst is with regard to particularly necessary.
The present invention be successfully prepared by way of hydro-thermal and high temperature pyrolysis under alkaline condition have excellent catalytic activity,
The Fe/N/C codope catalyst of stability and methanol tolerance performance, the preparation method is simple and convenient, and raw material is easy to get.
Summary of the invention
To solve the above problems, an object of the present invention is to provide a kind of Fe/N/C codope elctro-catalyst preparation side
Method, this method preparation process is simple, raw material is easy to get and inexpensively, has practical application potentiality.
The second object of the present invention is to provide the application of the Fe/N/C codope elctro-catalyst, that is, it is used for the yin of fuel cell
Pole hydrogen reduction process, the ORR take-off potential relative to reversible hydrogen electrode are 0.963V, half wave potential 0.821V, through durable
Property test after half wave potential only reduce 7mV, be provided simultaneously with excellent methanol tolerance performance.
To achieve the above objectives, the specific technical solution that the present invention takes are as follows:
1. a kind of preparation method of the Fe/N/C codope elctro-catalyst for efficient oxygen reduction reaction comprising the steps of:
(1) by 1.0 g carbon blacks, (XC-72, specific surface area are 235 m2 g-1) be put into 6 mol/L nitric acid solutions, heating water bath,
Flow back 48 h at 80 DEG C, then filters, and secondary water washing three times, is put in a vacuum drying oven, and 60 DEG C of drying are fully ground
It is placed in spare at dry.
(2) the pretreated carbon black of 40 mg, 1.60 g glucose are taken, 20 mg dodecyl sodium sulfates are dissolved into 20 ml
In secondary water, 4 h are ultrasonically treated, uniform black suspension is formed, ferric nitrate is then added, transfer the solution into hydro-thermal reaction
In kettle, setting oven temperature be 180 DEG C, the reaction time be 15 h, naturally cool to room temperature, filter, secondary water washing three times,
It is dried at 60 DEG C of vacuum oven, obtains black powder after being fully ground.
(3) it takes above-mentioned black powder sample (intermediate product) and melamine to be sufficiently mixed to be placed in tube furnace, nitrogen
High temperature pyrolysis under atmosphere obtains black solid powder.
The additional amount of step (2) described ferric nitrate is 0.5 ~ 1.5 mmol；
Mass ratio 1:5 ~ 10 of step (3) intermediate product and melamine；
Pyrolysis temperature is 800 ~ 1000 DEG C under step (3) described nitrogen atmosphere, and pyrolysis time is 1 h, heating rate 10
℃/min。
2. with a kind of answering for Fe/N/C codope elctro-catalyst for efficient oxygen reduction reaction of above-mentioned steps preparation
With steps are as follows:
Hydrogen reduction (ORR) performance test is carried out on electrochemical workstation to be coated with using the three-electrode system of standard
The glass-carbon electrode of Fe/N/C codope elctro-catalyst is working electrode, and platinum plate electrode is to electrode, and calomel electrode is reference electrode；
0.1mol/L potassium hydroxide solution is electrolyte；Five mouthfuls of glass electrolytic cells of tradition are reaction unit.Test result shows that it is opposite
It is 0.963V in the ORR take-off potential of reversible hydrogen electrode, half wave potential 0.821V, half wave potential only drops after durability test
Low 7mV is provided simultaneously with excellent methanol tolerance performance.
The glass-carbon electrode coated with Fe/N/C codope elctro-catalyst the preparation method is as follows:
5mg Fe/N/C codope elctro-catalyst powder is weighed, is added in 0.5ml aqueous isopropanol, ultrasonic disperse 1h is obtained
Uniform black slurries extract 10 μ l slurries with microsyringe, coated on clean glassy carbon electrode surface, then take 10 μ l
Nafion solution (Nafion solution of 10 μ l, 0.5 wt. % is dissolved into 1.0ml isopropanol) is coated in catalyst surface, red
It is dried under outer lamp to get the glass-carbon electrode coated with Fe/N/C codope elctro-catalyst is arrived.
Beneficial achievement of the invention:
The present invention provides a kind of preparation method of Fe/N/C codope elctro-catalyst and its in fuel cell oxygen reduction
Using, compared with other oxygen reduction catalysts, with simple, the cheap feature of preparation process, at the same with traditional quotient
Industry Pt/C catalyst is compared, catalytic performance can compare favourably therewith, half wave potential relative to the only low 36mV of reversible hydrogen electrode,
It is better than Pt/C catalyst in durability and methanol tolerance aspect of performance.These excellent performance gains are in the codope of Fe/N element
It changes the electronic structure of carbon nanomaterial and improves electric conductivity, provided for electronics transfer transmitting in catalytic process good
Channel is conducive to the absorption and disengaging of intermediate product, accelerates mass transfer velocity.Preparation method provided by the present invention is easily achieved
Industrially scalable application has certain meaning to entreprise cost society energy consumption is reduced, also to design and develop base metal oxygen also
Raw catalyst provides new selection.
Detailed description of the invention
Fig. 1: the sample ID prepared under different condition.
Fig. 2: a, b Fe0.5The transmission electron microscope picture of NC-900-2；C, d is Fe1.5The transmission electron microscope picture of NC-900-2；E, f is
Fe2.5The transmission electron microscope picture of NC-900-2.
Fig. 3: a Fe1.5The transmission electron microscope picture of NC-600-2；B is Fe1.5The transmission electron microscope picture of NC-700-2；C is
Fe1.5The transmission electron microscope picture of NC-800-2；D is Fe1.5The transmission electron microscope picture of NC-1000-2.
Fig. 4: line (a-e) is respectively Fe1.5The XRD spectrum of NC-T-2 (T=600,700,800,900,1000),
Line (f-g) is FexNC-900-2(X=0.5,2.5) XRD spectrum.
Fig. 5: Fe1.5NC-900-1、Fe1.5NC-900-2 and Fe1.5The x-ray photoelectron spectroscopy of NC-900-3, a, c and e points
It Wei not corresponding total spectrogram；B, d, f are respectively corresponding N1s spectrogram.
Fig. 6: a Fe0.5NC-900-2、Fe1.5NC-900-2 and Fe2.5The linear sweep voltammetry curve of NC-900-2；B is
Fe1.5NC-600-2、Fe1.5NC-700-2、Fe1.5NC-800-2、Fe1.5NC-900-2、Fe1.5NC-1000-2's and Pt/C is linear
Scan volt-ampere curve；C is Fe1.5NC-900-1、Fe1.5NC-900-2 and Fe1.5The linear sweep voltammetry curve of NC-900-3.
Fig. 7: a Fe1.5Linear sweep voltammetry curve comparison of the NC-900-2 after 1000 circle cyclic voltammetrics；B is Pt/C
Linear sweep voltammetry curve comparison after 1000 circle cyclic voltammetrics；C is Fe1.5NC-900-2 methanol tolerance linear scan
Volt-ampere curve comparison；D is Pt/C methanol tolerance linear sweep voltammetry curve comparison；E is Fe1.5NC-900-2 and Pt/C is used
The methanol tolerance of chronoamperometry compares, f Fe1.5NC-900-2 and Pt/C linear scan after 1000 circle cyclic voltammetrics
Volt-ampere curve comparison.
Specific embodiment
The present invention is further made explanations and illustrated below by way of specific embodiment and in conjunction with attached drawing.
Carbon black used in embodiment (XC-72) before the use, passes through following pretreatment: by 1.0 g carbon black (XC-
72, specific surface area is 235 m2 g-1) be put into 6 mol/L nitric acid solutions, heating water bath, flow back 48 h at 80 DEG C, then
Filter, secondary water washing three times, puts in a vacuum drying oven, 60 DEG C of drying, be fully ground be placed in it is spare at dry.
Embodiment 1:
(1) the pretreated carbon black of 40 mg, 1.60 g glucose are taken, 20 mg dodecyl sodium sulfates are dissolved into 20 ml bis- times
In water, 4 h are ultrasonically treated, uniform black suspension is formed, 0.5 mmol ferric nitrate is then added, transfers the solution into hydro-thermal
In reaction kettle, setting oven temperature is 180 DEG C, and the reaction time is 15 h, naturally cools to room temperature, is filtered, secondary water washing three
It is secondary, it is dried at 60 DEG C of vacuum oven, obtains black powder after being fully ground.
(2) it takes 80 mg black powder samples (intermediate product) and 800 mg melamines to be sufficiently mixed and is placed on tubular type
In furnace, the mass ratio of the two is 1:10, and high temperature pyrolysis under nitrogen atmosphere, pyrolysis temperature is 900 DEG C, 1 h of time, heating rate
For 10 DEG C/min, black solid powder is obtained, Fe is denoted as0.5NC-900-2。
Embodiment 2:
(1) the pretreated carbon black of 40 mg, 1.60 g glucose are taken, 20 mg dodecyl sodium sulfates are dissolved into 20 ml bis- times
In water, 4 h are ultrasonically treated, uniform black suspension is formed, 1.5 mmol ferric nitrates is then added, transfer the solution into hydro-thermal
In reaction kettle, setting oven temperature is 180 DEG C, and the reaction time is 15 h, naturally cools to room temperature, is filtered, secondary water washing three
It is secondary, it is dried at 60 DEG C of vacuum oven, obtains black powder after being fully ground.
(2) it takes 80 mg black powder samples (intermediate product) and 800 mg melamines to be sufficiently mixed and is placed on tubular type
In furnace, the mass ratio of the two is 1:10, and high temperature pyrolysis under nitrogen atmosphere, pyrolysis temperature is 900 DEG C, 1 h of time, heating rate
For 10 DEG C/min, black solid powder is obtained, Fe is denoted as1.5NC-900-2。
Embodiment 3:
(1) the pretreated carbon black of 40 mg, 1.60 g glucose are taken, 20 mg dodecyl sodium sulfates are dissolved into 20 ml bis- times
In water, 4 h are ultrasonically treated, uniform black suspension is formed, 2.5 mmol ferric nitrates is then added, transfer the solution into hydro-thermal
In reaction kettle, setting oven temperature is 180 DEG C, and the reaction time is 15 h, naturally cools to room temperature, is filtered, secondary water washing three
It is secondary, it is dried at 60 DEG C of vacuum oven, obtains black powder after being fully ground.
(2) it takes 80 mg black powder samples (intermediate product) and 800 mg melamines to be sufficiently mixed and is placed on tubular type
In furnace, the mass ratio of the two is 1:10, and high temperature pyrolysis under nitrogen atmosphere, pyrolysis temperature is 900 DEG C, 1 h of time, heating rate
For 10 DEG C/min, black solid powder is obtained, Fe is denoted as2.5NC-900-2。
Embodiment 4:
(1) the pretreated carbon black of 40 mg, 1.60 g glucose are taken, 20 mg dodecyl sodium sulfates are dissolved into 20 ml bis- times
In water, 4 h are ultrasonically treated, uniform black suspension is formed, 1.5 mmol ferric nitrates is then added, transfer the solution into hydro-thermal
In reaction kettle, setting oven temperature is 180 DEG C, and the reaction time is 15 h, naturally cools to room temperature, is filtered, secondary water washing three
It is secondary, it is dried at 60 DEG C of vacuum oven, obtains black powder after being fully ground.
(2) it takes 80 mg black powder samples (intermediate product) and 800 mg melamines to be sufficiently mixed and is placed on tubular type
In furnace, the mass ratio of the two is 1:10, and high temperature pyrolysis under nitrogen atmosphere, pyrolysis temperature is 600 DEG C, 1 h of time, heating rate
For 10 DEG C/min, black solid powder is obtained, Fe is denoted as1.5NC-600-2。
Embodiment 5:
(1) the pretreated carbon black of 40 mg, 1.60 g glucose are taken, 20 mg dodecyl sodium sulfates are dissolved into 20 ml bis- times
In water, 4 h are ultrasonically treated, uniform black suspension is formed, 1.5 mmol ferric nitrates is then added, transfer the solution into hydro-thermal
In reaction kettle, setting oven temperature is 180 DEG C, and the reaction time is 15 h, naturally cools to room temperature, is filtered, secondary water washing three
It is secondary, it is dried at 60 DEG C of vacuum oven, obtains black powder after being fully ground.
(2) it takes 80 mg black powder samples (intermediate product) and 800 mg melamines to be sufficiently mixed and is placed on tubular type
In furnace, the mass ratio of the two is 1:10, and high temperature pyrolysis under nitrogen atmosphere, pyrolysis temperature is 700 DEG C, 1 h of time, heating rate
For 10 DEG C/min, black solid powder is obtained, Fe is denoted as1.5NC-700-2。
Embodiment 6:
(1) the pretreated carbon black of 40 mg, 1.60 g glucose are taken, 20 mg dodecyl sodium sulfates are dissolved into 20 ml bis- times
In water, 4 h are ultrasonically treated, uniform black suspension is formed, 1.5 mmol ferric nitrates is then added, transfer the solution into hydro-thermal
In reaction kettle, setting oven temperature is 180 DEG C, and the reaction time is 15 h, naturally cools to room temperature, is filtered, secondary water washing three
It is secondary, it is dried at 60 DEG C of vacuum oven, obtains black powder after being fully ground.
(2) it takes 80 mg black powder samples (intermediate product) and 800 mg melamines to be sufficiently mixed and is placed on tubular type
In furnace, the mass ratio of the two is 1:10, and high temperature pyrolysis under nitrogen atmosphere, pyrolysis temperature is 800 DEG C, 1 h of time, heating rate
For 10 DEG C/min, black solid powder is obtained, Fe is denoted as1.5NC-800-2。
Embodiment 7:
(1) the pretreated carbon black of 40 mg, 1.60 g glucose are taken, 20 mg dodecyl sodium sulfates are dissolved into 20 ml bis- times
In water, 4 h are ultrasonically treated, uniform black suspension is formed, 1.5 mmol ferric nitrates is then added, transfer the solution into hydro-thermal
In reaction kettle, setting oven temperature is 180 DEG C, and the reaction time is 15 h, naturally cools to room temperature, is filtered, secondary water washing three
It is secondary, it is dried at 60 DEG C of vacuum oven, obtains black powder after being fully ground.
(2) it takes 80 mg black powder samples (intermediate product) and 800mg melamine to be sufficiently mixed and is placed on tube furnace
In, the mass ratio of the two is 1:10, and high temperature pyrolysis under nitrogen atmosphere, pyrolysis temperature is 1000 DEG C, 1 h of time, and heating rate is
10 DEG C/min, black solid powder is obtained, Fe is denoted as1.5NC-1000-2。
Embodiment 8:
(1) the pretreated carbon black of 40 mg, 1.60 g glucose are taken, 20 mg dodecyl sodium sulfates are dissolved into 20 ml bis- times
In water, 4 h are ultrasonically treated, uniform black suspension is formed, 1.5 mmol ferric nitrates is then added, transfer the solution into hydro-thermal
In reaction kettle, setting oven temperature is 180 DEG C, and the reaction time is 15 h, naturally cools to room temperature, is filtered, secondary water washing three
It is secondary, it is dried at 60 DEG C of vacuum oven, obtains black powder after being fully ground.
(2) it takes 80 mg black powder samples (intermediate product) and 400 mg melamines to be sufficiently mixed and is placed on tubular type
In furnace, the mass ratio of the two is 1:5, and high temperature pyrolysis under nitrogen atmosphere, pyrolysis temperature is 900 DEG C, 1 h of time, and heating rate is
10 DEG C/min, black solid powder is obtained, Fe is denoted as1.5NC-900-1。
Embodiment 9:
(1) the pretreated carbon black of 40 mg, 1.60 g glucose are taken, 20 mg dodecyl sodium sulfates are dissolved into 20 ml bis- times
In water, 4 h are ultrasonically treated, uniform black suspension is formed, 1.5 mmol ferric nitrates is then added, transfer the solution into hydro-thermal
In reaction kettle, setting oven temperature is 180 DEG C, and the reaction time is 15 h, naturally cools to room temperature, is filtered, secondary water washing three
It is secondary, it is dried at 60 DEG C of vacuum oven, obtains black powder after being fully ground.
(2) it takes 80 mg black powder samples (intermediate product) and 1200 mg melamines to be sufficiently mixed and is placed on tubular type
In furnace, the mass ratio of the two is 1:15, and high temperature pyrolysis under nitrogen atmosphere, pyrolysis temperature is 900 DEG C, 1 h of time, heating rate
For 10 DEG C/min, black solid powder is obtained, Fe is denoted as1.5NC-900-3。
As shown in Figure 1, listing the preparation condition difference of different samples in order to distinguish.
As shown in Fig. 2, carbon black degree of overlapping is higher in Fig. 2 a shows velveteen shape, apparent active particle is not observed, only
There is black reunion, can be seen that atomic arrangement is very chaotic by Fig. 2 b, spacing of lattice is shown as 0.209 nm；With molysite forerunner
The increase of object, the clear spacing of lattice of atomic arrangement are 0.206 nm, the Fe for being 0.204 nm very close to spacing of lattice3N's
(111) crystal face；When molysite increases to 2.5 mmol, formed there are many non-uniform bulk metal compound, spacing of lattice is
0.298 nm, corresponding Fe2O3(220) crystal face.
As shown in figure 3, the catalyst sample pattern prepared under different pyrolysis temperatures is significantly different, with pyrolysis temperature
Increased activity amounts of particles gradually increases and more uniformly, but occurs when pyrolysis temperature is increased to 1000 DEG C non-uniform big
Block metallic compound.
As shown in figure 4, XRD diffraction maximum corresponds respectively to Fe at 29.7 °, 40.8 °, 43.4 °, 57.0 °3N(PDF#49-
1662) (101), (002), (111), (112) crystal face and the peak detected at 30.2 °, 35.6 °, 57.3 °, 62.9 ° difference
Corresponding to Fe2O3(PDF#39-1346) (220), (311), (422), (440) crystal face, the phenomenon table in conjunction with shown in Fig. 2 and Fig. 3
The bright catalyst is made of carbon, iron oxide and nitrided iron.
As shown in figure 5, Fig. 5 a, 5c and 5e are Fe respectively1.5NC-900-1, Fe1.5NC-900-2 and Fe1.5NC-900-3
The total spectrogram of XPS, further demonstrate the catalyst and be made of C, N, O and Fe element；By comparing the N1s of three kinds of catalyst
Map, it can be seen that in five kinds of different type nitrogen, graphite nitrogen and nitrogen " iron " account for 40 ~ 60%, and the nitrogen of both types exists
Fe1.5Other two kinds of catalyst are apparently higher than in NC-900-2, this may be the weight for causing the catalyst to have excellent properties
Want reason.
As shown in fig. 6, compared with other catalyst, Fe1.5NC-900-2 shows optimal catalytic activity, with business
Pt/C catalyst is compared, and only low 30 mV has reached 821 mV(relative to reversible hydrogen electrode to half wave potential).
As shown in fig. 7, Fig. 7 a is shown in after the CV test of 1000 circles, Fe1.5NC-900-2 half wave potential reduced by only
Half wave potential is greatly reduced business Pt/C catalyst under identical testing conditions in 7 mV, Fig. 7 b, reaches 60 mV, will test
Linear volt-ampere curve afterwards compares (Fig. 7 f), it can be seen that Fe1.5The half wave potential of NC-900-2 is higher by than business Pt/C
18 mV；Fig. 7 c and 7d are Fe respectively1.5The methanol tolerance performance test of NC-900-2 and business Pt/C, comparing result show prepared
Fe1.5There is NC-900-2 excellent methanol tolerance performance to adopt simultaneously to further prove the methanol tolerance performance of the catalyst
It is tested (Fig. 7 e) with i-t method, as the result is shown Fe1.5Fluctuation NC-900-2 only small after methanol is added dropwise, 1000
Still maintain 92% electric current after s, and business Pt/C fluctuation, electric current is only 54% at the end of test.These test results are equal
Show Fe1.5NC-900-2 has excellent ORR catalytic performance.
Claims (9)
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