CN108374179B - A kind of preparation method and application of the compound nitrogen-doped carbon material of two cobaltous selenide of Fe2O3 doping - Google Patents
A kind of preparation method and application of the compound nitrogen-doped carbon material of two cobaltous selenide of Fe2O3 doping Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 8
- -1 cobaltous selenide Chemical class 0.000 title abstract description 7
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 title abstract description 6
- 150000001875 compounds Chemical class 0.000 title abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 33
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 33
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000007772 electrode material Substances 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 9
- 239000002002 slurry Substances 0.000 claims abstract description 8
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000004917 carbon fiber Substances 0.000 claims abstract description 4
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 4
- 239000011669 selenium Substances 0.000 claims abstract description 4
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 3
- 238000011068 loading method Methods 0.000 claims abstract 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 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 claims description 18
- 238000005868 electrolysis reaction Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000003763 carbonization Methods 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 239000012159 carrier gas Substances 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000006228 supernatant Substances 0.000 claims description 2
- GAIMSHOTKWOMOB-UHFFFAOYSA-N [Se]=[Co]=[Se] Chemical compound [Se]=[Co]=[Se] GAIMSHOTKWOMOB-UHFFFAOYSA-N 0.000 claims 5
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims 3
- 239000002244 precipitate Substances 0.000 claims 3
- 239000002033 PVDF binder Substances 0.000 claims 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims 2
- 229910021094 Co(NO3)2-6H2O Inorganic materials 0.000 claims 1
- 229910016870 Fe(NO3)3-9H2O Inorganic materials 0.000 claims 1
- 229910000608 Fe(NO3)3.9H2O Inorganic materials 0.000 claims 1
- 239000004480 active ingredient Substances 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 9
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 abstract description 5
- 229910001447 ferric ion Inorganic materials 0.000 abstract description 5
- 230000001680 brushing effect Effects 0.000 abstract description 4
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 238000013112 stability test Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000012621 metal-organic framework Substances 0.000 abstract 1
- 230000001681 protective effect Effects 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000010189 synthetic method Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 11
- 235000019441 ethanol Nutrition 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003245 coal Substances 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
- 239000000470 constituent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012453 solvate Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- 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
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- 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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention discloses a kind of preparation method and applications of compound nitrogen-doped carbon material of two cobaltous selenide of Fe2O3 doping.This method is using metal organic framework ZIF-67 as presoma, it etches to obtain the Fe-ZIF-67 of iron modification using ferric ion, Fe-ZIF-67 is subjected to charing and selenizing with selenium steam at high temperature, obtains the two cobaltous selenide (Fe-CoSe of Fe2O3 doping of N doping porous carbon load2@NC) powdered electrode material.By Fe-CoSe2@NC powder is made slurry brushing and Fe-CoSe is made on conductive paper of carbon fiber2@NC/CFP electrode.Fe-CoSe2The electrochemical catalysis H2-producing capacity index of@NC/CFP electrode are as follows: Tafel slope is 40.9mV/decade；Reach 10mA/cm2The overpotential of current density is -0.143V (vs RHE).Meanwhile there is this group of loading electrode excellent electrochemical stability apparent voltage fluctuation do not occur in 48 hours constant current stability tests.The combination electrode synthetic method is simple and efficient, is environmentally protective, and raw material and synthesis cost are low, is suitble to the industrial application of electrochemical decomposition aquatic products hydrogen, has extensive scientific meaning.
Description
Technical field
The present invention relates to a kind of electrocatalytic decomposition water combination electrode more particularly to a kind of efficient electrocatalytic decomposition aquatic products hydrogen are multiple
The preparation method and application of composite electrode, belong to water electrolysis hydrogen production field.
Background technique
With growing, serious environmental pollution and the future source of energy danger of the fossil energy consumptions amount such as global coal, petroleum
Machine is that the mankind must problems faced.Efficient, reproducible clean energy resource is developed, such as solar energy, wind energy, water energy, biomass
Energy and thus derivative electric energy, it is extremely urgent to improve its ratio in entire energy resource structure.In numerous new energies,
How to realize new energy storage and it is without interruption be a very crucial problem, wherein being translated into chemical energy is one
Main approach, such as electrolysis water hydrogen manufacturing.Efficient electrolysis aquatic products hydrogen catalyst is developed for improving water electrolysis hydrogen production process
The utilization efficiency of the middle energy is most important, so far, most efficiently produce hydrogen catalyst be noble metal platinum, but its high cost and
Scarcity limits its large-scale application in water electrolysis hydrogen production reaction.And it is based on the chemical combination of transition metal (iron, cobalt, nickel etc.)
Object presents good potential in electrolysis aquatic products hydrogen field, and cheap price and relatively high catalytic activity cause research people
The extensive concern of member.Therefore, to prepare cheap, efficient, stable transistion metal compound with a kind of simple method expensive to substitute
Metal platinum produces hydrogen material as electrode catalyst, is a job with important research meaning at present.
Summary of the invention
Problem to be solved by this invention is just to provide a kind of using simple mild preparation method, synthesizing efficient, cost
The electrolysis water catalysis low, stability is good produces hydrogen electrode material.
Another object of the present invention is to provide the preparation methods of electrolysis aquatic products hydrogen composite catalyzing electrode material.
The present invention has one to be designed to provide application method of the powdery electrode material in acidic electrolysis aquatic products hydrogen again.
The present invention mainly adopts the following technical scheme that realization:
A kind of preparation method of the compound nitrogen-doped carbon material of two cobaltous selenide of Fe2O3 doping, includes the following steps:
1) prepared by ZIF-67: by Co (NO3)2·6H2O and 2-methylimidazole are dissolved in methanol solvate respectively, room temperature condition
Lower mixing reaction, raw empurpled precipitating, as product ZIF-67 wash ZIF-67 precipitating repeatedly until being clarified
Colourless supernatant, sediment is centrifugated, drying for standby；
2) prepared by Fe-ZIF-67: by Fe (NO3)3·9H2O is dissolved in ethyl alcohol or water that obtain the ethyl alcohol containing ferric nitrate molten
Liquid or aqueous solution containing ferric nitrate；It takes product ZIF-67 obtained in step 1) to be dispersed in ethyl alcohol or water, slowly adds
Enter the ethanol solution containing ferric nitrate or the aqueous solution containing ferric nitrate, and stir, utilizes Fe3+The Hydrogen Proton etching that hydrolysis generates
ZIF-67 releases Co2+, with the consumption of Hydrogen Proton, Fe3+And Co2+Co-precipitation occurs on ZIF-67 particle, obtains iron modification
Fe-ZIF-67；
3)Fe-CoSe2@NC preparation: by Fe-ZIF-67 powder obtained in step 2) using selenium steam at 350-500 DEG C
Under the conditions of carry out charing and selenizing, obtain black powder N doping porous carbon load two cobaltous selenide combination electrode of Fe2O3 doping
Material, i.e. Fe-CoSe2@NC electrode material.
Preferably, in the step 1), Co (NO3)2·6H2The molar ratio range of O and 2-methylimidazole is 1:1-1:16,
Reaction time is 6-24 hours.
Preferably, the ZIF-67 and Fe (NO3)3·9H2The mass ratio of O is 2:1-8:1.
Preferably, in the step 3), charing and selenizing carry out in tube furnace, and selenizing charing is to carry with inert gas
Gas, selenizing carbonization condition be 400 DEG C reaction 1-4 hours.
The invention also discloses a kind of Fe-CoSe2The preparation method of@NC/CFP electrode, by the Fe-CoSe of preparation2@NC electricity
Slurry is made in pole material hybrid conductive carbon black, Kynoar dispersion, and slurry is uniformly brushed on conductive paper of carbon fiber, dry
Obtain Fe-CoSe2@NC/CFP electrode.
Preferably, Fe-CoSe2@NC dusty material and conductive black, Kynoar are according to mass ratio 1:(0.125-1):
(0.125-0.5) mixing, the upper Fe-CoSe of CFP2@NC effective active composition load capacity is 0.2-1mg/cm2。
Preferably, the drying process carries out under the conditions of 50 DEG C, and drying time is 12 hours.
The invention also discloses Fe-CoSe2Application of the@NC/CFP electrode in electrolysis aquatic products hydrogen.In 0.5MH2SO4Electrolysis
The electrochemistry carried out in liquid produces hydrogen test result and shows Fe-CoSe2@NC/CFP composite catalyzing electrode has high production hydrogen activity,
It, which is catalyzed, generates 10mA/cm2Current density only need the overpotential of -0.143V (vs.RHE), and surveyed in 48 hours constant currents
Excellent stability is shown during examination.
Compared with the existing technology, the invention has the following advantages that
1.Fe-CoSe2@NC/CFP water electrolysis hydrogen production overpotential is low, 10mA/cm2Overpotential is only -143mV.
2.Fe-CoSe2@NC/CFP water electrolysis hydrogen production Tafel slope is low, only 40.9mV/dec, slightly above noble metal platinum
(30mV/dec), lower Tafel slope illustrates that material can generate bigger electric current to drive under lower overpotential, to produce
Raw more hydrogen, improve the utilization efficiency of the energy.
3. electrode material synthesis technology is simple, reaction condition is mild, catalyst Fe-CoSe2@NC can be by being made slurry
Electrode use is made in brushing in conductive substrates, and process flow is simply controllable, is conducive to industrial operation.
Detailed description of the invention
Fig. 1 shows the ZIF-67 shape appearance figure that embodiment 2 passes through scanning electron microscopic observation；
Fig. 2 shows the Fe-ZIF-67 shape appearance figures that embodiment 2 passes through scanning electron microscopic observation；
Fig. 3 shows Fe-CoSe of the embodiment 2 by scanning electron microscopic observation2@NC shape appearance figure；
Fig. 4 shows ZIF-67, Fe-CoSe in embodiment 22@NC and CoSe2The crystalline state and crystalline structure of@NC characterizes；
Fig. 5 shows the Fe-CoSe in embodiment 42@NC/CFP and CoSe2@NC/CFP electrode linear scan volt-ampere curve；
Fig. 6 shows the Fe-CoSe in embodiment 42@NC/CFP and CoSe2The Tafel curve of@NC/CFP electrode；
Fig. 7 shows the Fe-CoSe in embodiment 42The current versus time curve of@NC/CFP electrode stability test；
Fig. 8 shows hydrogen actual production and theoretical yield versus time curve in embodiment 5.
Specific embodiment
Embodiment 1
The carbon fiber paper for being 2 square centimeters by geometric area successively spends dilute hydrochloric acid, ethyl alcohol, deionized water ultrasonic cleaning
30 minutes, remove the impurity such as metal ion and the organic matter on surface.Place in an oven, 50 DEG C drying 12 hours, it is spare.
Embodiment 2
ZIF-67 is prepared using solution deposit first, by 8mmol 2-methylimidazole and 2mmol cabaltous nitrate hexahydrate point
It is not dissolved in dissolution in 50ml methanol solution and obtains clear solution, is then stirred to react two kinds of solution mixed room temperatures 24 hours.
Then by reaction product centrifugation, washing, drying, pattern picture such as Fig. 1 institute of solid purple powder ZIF-67, ZIF-67 are obtained
Show, shows the granatohedron structure of standard.It takes 40mg ZIF-67 powder to be dispersed in 20ml ethanol solution, adds
Enter 5ml ferric nitrate ethanol solution (2mg/ml), is stirred to react under room temperature two hours, ZIF-67 is in Fe3+Hydrolyze the hydrogen generated
The corrasion of ion releases Co2+, with the consumption of Hydrogen Proton, Fe3+And Co2+Co-precipitation obtains iron on ZIF-67 particle
Then reaction product is centrifuged, is washed, is dried to obtain the solid powder Fe-ZIF-67 of purple, pattern by the Fe-ZIF-67 of modification
For picture as shown in Fig. 2, Fe-ZIF-67 maintains granatohedron structure, particle surface becomes coarse after etching.Then will
Fe-ZIF-67 uniformly spreads and is dispersed in porcelain boat, is put into tube furnace, using 100sccm argon gas as carrier gas, using selenium steam as reaction gas,
Two hours of high temperature selenizing are carried out under the conditions of 400 DEG C, obtain Fe-CoSe2@NC electrode material, pattern picture is as shown in figure 3, list
A Fe-CoSe2@NC particle still maintains granatohedron structure, and surface becomes more coarse.As a comparison, will not have
There is etched ZIF-67 powder to carry out same selenization, directly two hours of high temperature selenizing under the conditions of 400 DEG C, obtains
CoSe2@NC electrode material is with Fe-CoSe2@NC has similar pattern.ZIF-67,Fe-CoSe2@NC and CoSe2The crystallization of@NC
State and crystalline structure are as shown in figure 4, wherein Fe-CoSe2@NC and CoSe2Contain the good oblique cubic phase of crystallinity in@NC
Two cobaltous selenide crystal.
Embodiment 3
The above-mentioned Fe-CoSe that will be prepared2@NC dusty material and conductive black, Kynoar are according to mass ratio 5:4:1
Mixing is made slurry brushing with ethyl alcohol reconciliation and Fe-CoSe is made on CFP2@NC/CFP electrode, dry 12 under the conditions of 50 DEG C
Hour.By CoSe2@NC electrode material loads on CFP according to same ratio and brushing method, prepares CoSe2@NC/CFP electricity
Pole.Wherein Fe-CoSe2@NC and CoSe2Load capacity of the@NC active constituent on CFP is 0.5mg/cm2。
Embodiment 4
Using the electrochemical workstation of three-electrode system, the Fe-CoSe that will be prepared as described in Example 32@NC/CFP electrode
And CoSe2@NC/CFP electrode is as working electrode, and graphite rod is to electrode, and Ag/AgCl electrode is reference electrode, and electrolyte is
0.5M H2SO4Solution.Polarization curve sweep interval arrives -0.6V (vs.Ag/AgCl) for 0, sweep speed 3mV/s, Different electrodes
Polarization result as shown in figure 5, the Tafel curve that is calculated by polarization curve as shown in fig. 6, production hydrogen test result in figure
Show Fe-CoSe2@NC/CFP electrode reaches 10mA/cm2Current density only need -0.143V (vs.RHE), and it is undoped
CoSe2@NC/CFP electrode reaches 10mA/cm2Current density needs -0.173V (vs.RHE), Fe-CoSe2@NC/CFP electrode
And CoSe2The production hydrogen Tafel slope of@NC/CFP electrode is respectively 40.9mV/dec and 69.2mV/dec, therefore, Fe-CoSe2@
The H2-producing capacity of NC/CFP electrode is compared to CoSe2@NC/CFP electrode is obviously improved.Fe-CoSe2@NC/CFP electrode exists
10mA/cm2Under the conditions of constant current stability test data as shown in fig. 7, in 48 hours constant current test process, Fe-CoSe2@
The overpotential of NC/CFP electrode does not fluctuate significantly, shows good electrochemical stability.According to DFT theoretical calculation point
Analysis, Fe-CoSe2Crystal and CoSe2The production hydrogen activity site of crystal is mainly Co atom, and Fe-CoSe2The site Co in crystal
Reactive hydrogen adsorption free energy ratio CoSe2The site Co in crystal can accelerate the mistake being electrolysed in aquatic products hydrogen closer to zero
Cross the adsorption desorption process of state hydrogen, therefore Fe-CoSe2With higher catalytic activity.Embodiment 5
As described in Example 4, using the electrochemical workstation of three-electrode system, Fe-CoSe2@NC/CFP electrode is as work
Make electrode, graphite rod is to electrode, and Ag/AgCl electrode is reference electrode, and electrolyte is 0.5M H2SO4Solution.Electrolyte continues
It exposes into 30 minutes N2Oxygen in exclusion system is continually fed into nitrogen in test process.Apply 10mA constant current, every 30 minutes
A gas is taken, with hydrogen output in gas-chromatography test enclosed system.The curve that the yield of hydrogen changes over time such as Fig. 8,
Its practical hydrogen output measured is essentially identical to theoretical calculation yield, illustrates to be electrolysed during aquatic products hydrogen substantially without other pairs
Reaction occurs, Fe-CoSe2The current efficiency of@NC/CFP electrolysis aquatic products hydrogen is close to 100%.
Claims (8)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810123010.2A CN108374179B (en) | 2018-02-07 | 2018-02-07 | A kind of preparation method and application of the compound nitrogen-doped carbon material of two cobaltous selenide of Fe2O3 doping |
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