CN110038638A - A kind of iron load nitrogen-doped porous carbon material and its synthetic method and application with excellent electro-catalysis reduction nitrogen performance - Google Patents
A kind of iron load nitrogen-doped porous carbon material and its synthetic method and application with excellent electro-catalysis reduction nitrogen performance Download PDFInfo
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- CN110038638A CN110038638A CN201910412772.9A CN201910412772A CN110038638A CN 110038638 A CN110038638 A CN 110038638A CN 201910412772 A CN201910412772 A CN 201910412772A CN 110038638 A CN110038638 A CN 110038638A
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 96
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 50
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 45
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 43
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 38
- 230000009467 reduction Effects 0.000 title claims abstract description 22
- 238000010189 synthetic method Methods 0.000 title claims abstract description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 48
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 23
- 238000001354 calcination Methods 0.000 claims abstract description 22
- 239000000047 product Substances 0.000 claims abstract description 22
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 15
- 230000003213 activating effect Effects 0.000 claims abstract description 14
- 150000002460 imidazoles Chemical class 0.000 claims abstract description 10
- 150000003751 zinc Chemical class 0.000 claims abstract description 10
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 9
- 150000001298 alcohols Chemical class 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 238000007789 sealing Methods 0.000 claims abstract description 5
- 239000013049 sediment Substances 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 39
- 239000000463 material Substances 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 230000015572 biosynthetic process Effects 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 235000019441 ethanol Nutrition 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 239000010453 quartz Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001291 vacuum drying Methods 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
- 229920000557 Nafion® Polymers 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 230000005611 electricity Effects 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical group [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 238000002242 deionisation method Methods 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 239000006228 supernatant Substances 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 3
- 239000008367 deionised water Substances 0.000 abstract 1
- 229910021641 deionized water Inorganic materials 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 description 17
- 238000012360 testing method Methods 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 11
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 5
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000001603 reducing effect Effects 0.000 description 3
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 2
- 125000002883 imidazolyl group Chemical group 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 229910015183 FeNx Inorganic materials 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000011852 carbon nanoparticle Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method 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
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000007970 homogeneous dispersion Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 1
- WSSMOXHYUFMBLS-UHFFFAOYSA-L iron dichloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Fe+2] WSSMOXHYUFMBLS-UHFFFAOYSA-L 0.000 description 1
- -1 iron ion Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- B01J35/33—
-
- B01J35/60—
-
- 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
- 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
Abstract
The invention discloses a kind of iron load nitrogen-doped porous carbon material with excellent electro-catalysis reduction nitrogen performance and its synthetic method and application, synthetic methods are as follows: imidazoles substance is dissolved in alcohols solvent, forms solution A；Zinc salt and ferrous salt are dissolved in alcohols solvent, solution B is formed；Solution A and solution B are each led into after nitrogen drains air, sealing, is stood mixing, it is then centrifuged for isolated sediment, it clays into power after drying precipitate, calcining and activating again, calcined product is successively washed with hydrochloric acid solution, deionized water, is dried to obtain iron load nitrogen-doped porous carbon material product.Iron load nitrogen-doped porous carbon material of the invention is applied to stability with higher, NH when electro-catalysis ammonia synthesis reaction3Generating rate is up to 1.26ug/h/cm2, faradic efficiency can reach 0.66%.
Description
Technical field
The present invention relates to it is a kind of with excellent electro-catalysis reduction nitrogen performance iron load nitrogen-doped porous carbon material and its
Synthetic method and application.
Background technique
Recently as the increase of growth and the energy demand of world population, ammonia (NH3) it is not only widely used in chemical fertilizer production,
It and is considered as a kind of Hydrogen carrier being readily transported and ideal chemical hydrogen storage material.But due to N2Chemical inertness
With the energy barrier of high N ≡ N bond cleavage solution, NH3Synthesis depend on traditional Haber-Bosch technique, atmospheric nitrogen and H2In high temperature
Ammonia is synthesized under high pressure, which results in a large amount of energy consumption and greenhouse gas emissions.It is considered as a kind of ring that electro-catalysis, which synthesizes ammonia,
The solution of border close friend because it can by Reproduceable electricity provide electric power without will cause a large amount of Fossil fuel consumption and
CO2 emission.The strategy in a mild condition, uses water as hydrogen source instead of High Purity Hydrogen (H2) directly by N2It is converted into NH3。
The doped porous carbon material of transition metal load has the excellent performances such as at low cost, catalytic performance is good, easy preparation, environmental protection, transition
Metal (iron, cobalt ...) load Heteroatom doping porous carbon materials because of its earth rich reserves, have excellent performance and by extensive
Concern.
Summary of the invention
For the above-mentioned problems in the prior art, the object of the present invention is to provide it is easy to operate, cheap,
Product yield high, a kind of iron with excellent electro-catalysis nitrogen reducing property with biggish economy and practical value load nitrogen
Doped porous carbon material and its synthetic method and application.
A kind of synthesis side of the iron load nitrogen-doped porous carbon material with excellent electro-catalysis reduction nitrogen performance
Method, it is characterised in that include the following steps:
1) imidazoles substance is dissolved in alcohols solvent, forms solution A；Zinc salt and ferrous salt are dissolved in alcohols solvent, formed molten
Liquid B；Nitrogen 30 ~ seal after forty minutes is each led into solution A and solution B, then mixes the solution A of sealing and solution B, it is close
It is stored at room temperature under the conditions of envelope 8 ~ 12 hours；
2) after step 1) is stood, the mixed liquor after standing is placed in a centrifuge centrifuge separation, obtains supernatant and precipitating
Object；By grind into powder after sediment vacuum drying, save backup；
3) powder obtained by step 2 is put into quartz boat, quartz boat, which is placed on again in tube furnace, carries out calcining and activating, obtains black
Color powdered product；
4) black powder product obtained by step 3) is washed with hydrochloric acid solution to remove the zinc in black powder product, then uses deionization
Water washing is removed with the hydrochloric acid that will be adhered on black powder product, then in being dried in vacuum oven to get arriving the iron
Load nitrogen-doped porous carbon material product.
A kind of synthesis side of the iron load nitrogen-doped porous carbon material with excellent electro-catalysis reduction nitrogen performance
Method, it is characterised in that in step 1), the imidazoles substance is 2-methylimidazole, and the zinc salt is zinc nitrate or zinc chloride, institute
Stating ferrous salt is ferrous nitrate or frerrous chloride；The alcohols solvent is methanol or ethyl alcohol, preferably methanol.
A kind of synthesis side of the iron load nitrogen-doped porous carbon material with excellent electro-catalysis reduction nitrogen performance
Method, it is characterised in that in step 1), the amount of the total material of both zinc salt and ferrous salt and the ratio between the amount of substance of imidazoles substance
It is 0.5 ~ 1.5: 4, preferably 1: 4.
A kind of synthesis side of the iron load nitrogen-doped porous carbon material with excellent electro-catalysis reduction nitrogen performance
Method, it is characterised in that in step 2, it is 8000 ~ 10000rpm that mixed liquor, which is placed in a centrifuge the revolving speed being centrifuged, from
The time of heart separation is 8 ~ 12 minutes；In step 2, vacuum drying temperature is 60 ~ 80 DEG C, and drying time is 8 ~ 16 hours.
A kind of synthesis side of the iron load nitrogen-doped porous carbon material with excellent electro-catalysis reduction nitrogen performance
Method, it is characterised in that in step 3), the process of calcining and activating are as follows: under the conditions of nitrogen protection, from room temperature with 5 ~ 10 DEG C/min's
Rate is warming up to 500-900 DEG C, then calcining at constant temperature 1 ~ 4 hour again, subsequent cooled to room temperature.
A kind of synthesis side of the iron load nitrogen-doped porous carbon material with excellent electro-catalysis reduction nitrogen performance
Method, it is characterised in that in step 4), the concentration of the hydrochloric acid solution is 2 ~ 5mol/L, and the time with hydrochloric acid solution carrying out washing treatment is
6 ~ 8 hours；In step 4), the temperature being dried in vacuum oven is 80 ~ 100 DEG C, and drying time is 8 ~ 16 hours.
The iron load nitrogen-doped porous carbon material prepared according to the method described above.
Application of the iron load nitrogen-doped porous carbon material in electro-catalysis reduction nitrogen synthesis ammonia.
Application of the iron load nitrogen-doped porous carbon material in electro-catalysis reduction nitrogen synthesis ammonia, it is characterised in that
The following steps are included:
S1: iron load nitrogen-doped porous carbon material is mixed with the ethanol solution of Nafion, after ultrasonic disperse, by institute's score
Dispersion liquid is dripped on carbon paper, and then carbon paper electrode is made in drying in air；
S2: being to electrode, using acidic aqueous solution as electricity with platinum plate electrode using carbon paper electrode obtained by step S1 as working electrode
Liquid is solved, electrocatalytic reaction is carried out and synthesizes ammonia.
Compared with the existing technology, the beneficial effect that the present invention obtains is:
1) present invention is during preparing iron load nitrogen-doped porous carbon material, imidazoles substance solution and zinc salt, ferrous salt
Solution mixing, ferrous ion and zinc salt and imidazole group generate coordination, then after carrying out calcining and activating, the carbonization of imidazoles substance
Nitrogen-doped porous carbon material is formed, the nitrogen-doped porous carbon material forms organic metal framework material (ZIF- in conjunction with zinc salt
8) carbon frame, is provided for the iron atom of doping, and ferrous salt is reduced to iron simple substance by the carbon material that calcining and activating is formed.Due to Asia
The coordination of iron ion and imidazole group, during calcining and activating, iron atom is uniformly distributed in the carbon frame.
2) ZIF-8 has periodic pore structure, and this paper starting point increases catalyst also with the porous structure of ZIF-8
Specific surface area, active site iron atom is more advantageous to evenly dispersed on ZIF-8.Nitrogen in imidazoles substance can be with
Iron atom forms FeNx compound in high-temperature burning process, makees to play certain regulation to the reactivity of iron atom
With.Black powder product after calcining and activating is using the purpose that hydrochloric acid solution is washed: Zn-ef ficiency therein is removed, with
The porosity for increasing material is more advantageous to the catalytic activity for improving material.
3) for the present invention using metallic iron as source metal, earth rich reserves are cheap；Material is easily prepared, and makes
Standby process environmental pollution very little；Resulting materials electro-catalysis nitrogen reducing property is preferable, NH3Generating rate is up to 1.26ug/
h/cm2, faradic efficiency at this time is 0.66%.Iron load nitrogen-doped porous carbon material of the invention is synthesized applied to electro-catalysis
Stability with higher, application prospect are very extensive when ammonia reaction.
Detailed description of the invention
Fig. 1 is scanning electron microscopic picture of the Fe-N/C-800 material of the preparation of embodiment 1 under 10 μm；
Fig. 2 is transmission electron microscope picture of the Fe-N/C-800 material of the preparation of embodiment 1 at 50nm；
Fig. 3 is transmission electron microscope picture of the Fe-N/C-800 material of the preparation of embodiment 1 at 5nm；
Fig. 4 is that Fe-N/C-800 material prepared by embodiment 1 is being full of N20.1mol/L hydrochloric acid electrolyte in be electrolysed
The linear volt-ampere test curve figure of reaction；
Fig. 5 is that Fe-N/C-800 material of the present invention and N/C material are being full of N20.1mol/L hydrochloric acid electrolyte in carry out electricity
Solve the yield and faradic efficiency comparison diagram of reaction；
Fig. 6 is that Fe-N/C-800 material prepared by embodiment 1 is being full of N20.1mol/L hydrochloric acid electrolyte in be electrolysed
The cyclical stability test chart of reaction.
Specific embodiment
The present invention is further explained in the light of specific embodiments, but the scope of protection of the present invention is not limited thereto.
Embodiment 1:
The preparation of the nitrogen-doped porous carbon material Fe-N/C-800 of metallic iron load, includes the following steps:
1) 2-methylimidazole of 3280mg is dissolved in 50mL methanol, forms solution A；By 2677mg zinc nitrate hexahydrate and 198mg
Iron dichloride tetrahydrate is dissolved in 50mL methanol, forms solution B；It is close after each leading into nitrogen in solution A and solution B 30 minutes
Then envelope mixes the solution A of sealing and solution B, be stored at room temperature 12 hours under air-proof condition；
2) after step 1) is stood, the mixed liquor after standing is placed in a centrifuge and is centrifuged 10 minutes under 10000rpm revolving speed
After obtain sediment, behind at the sediment in a vacuum drying oven 80 DEG C dry 10 hours, grind into powder is saved standby
With；
3) powder obtained by step 2 is put into quartz boat, quartz boat, which is placed on again in tube furnace, carries out calcining and activating, and calcining is lived
The process of change are as follows: under the conditions of nitrogen protection, be warming up to 800 DEG C from room temperature with the rate of 7 DEG C/min, then calcining at constant temperature 2 again
Cooled to room temperature after hour, obtains black powder product；
4) black powder product obtained by step 3) is first washed 7 hours with 5mol/L hydrochloric acid solution, then is washed with deionized to incite somebody to action
Hydrochloric acid on black powder product is adhered to remove, then in vacuum oven at 90 DEG C dry 10 hours to get arriving iron
Load nitrogen-doped porous carbon material product (being labeled as Fe-N/C-800 material).
The scanning electron microscope (SEM) photograph of Fe-N/C-800 material prepared by embodiment 1 under 10 μm is as shown in Figure 1, prepared by embodiment 1
Fe-N/C-800 material at 50nm and 5nm transmission electron microscope picture difference it is as shown in Figures 2 and 3, can from Fig. 1, Fig. 2 and Fig. 3
To find out, Fe-N/C-800 material prepared by embodiment 1 remains the crystal structure of ZIF-8, and iron particle is by carbon nano-particle packet
It covers, which has the porous structure of ZIF-8, can increase the active site of reaction.In addition, the iron particle of carbon-coating cladding can be with
Stable structure is kept during the reaction.
Fe-N/C-800 material prepared by embodiment 1 synthesizes the application of ammonia for electro-catalysis: by 4mg's as catalyst
Fe-N/C-800 material, 0.9mL ethyl alcohol and 0.1mL Nafion solution (Nafion solution mass concentration is 5%) mixing, ultrasound point
It dissipates uniformly, homogeneous dispersion is dripped in 2 × 2cm2On the carbon paper of size, then carbon paper electrode is made in drying in air.With this
Carbon paper electrode is to electrode, using Ag/AgCl as reference electrode, 0.1mol/L hydrochloric acid solution with platinum plate electrode as working electrode
For electrolyte, it is assembled into the test device of nitrogen reducing catalyst, tests linear volt-ampere test curve (test condition are as follows: -0.8V
~ 0.2V, sweep speed 10mV/s, room temperature), testing linear volt-ampere test curve is the 0.1 mol/L HCl/water in nitrogen saturation
It is carried out in solution, as a result as shown in Figure 4.The catalytic activity for testing electro-catalysis reduction nitrogen synthesis ammonia, the 0.1 of nitrogen saturation
It is tested in mol/L HCL aqueous solution, test voltage is -0.70V ~ -0.45V, the yield of ammonia and faraday under different voltages
Efficiencies are as shown in Figure 5.The stability test of electro-catalysis reduction nitrogen synthesis ammonia is carried out under -0.55V voltage, it is full in nitrogen
It is tested in 0.1 mol/L HCL aqueous solution of sum, working electrode is recycled for multiple times, each testing time is 2 hours,
Test results are shown in figure 6 for the cyclical stability of reaction generation ammonia.From fig. 6 it can be seen that its NH3Generating rate is up to
1.26ug/h/cm2, and the yield of ammonia and faradic efficiency variation are smaller, illustrate that catalyst of the invention has preferable stability.
Embodiment 2:
The preparation of the nitrogen-doped porous carbon material Fe-N/C-500 of metallic iron load, repeats the Fe-N/C-800 material of embodiment 1
Process, the difference is that in step 3) calcining and activating process replacement are as follows: under the conditions of nitrogen protection, from room temperature with 7 DEG C/
The rate of min is warming up to 500 DEG C, then cooled to room temperature after calcining at constant temperature 2 hours again.Remaining step and 1 phase of embodiment
Together, finally obtain iron load nitrogen-doped porous carbon material product (labeled as Fe-N/C-500 material).
Fe-N/C-500 material prepared by embodiment 2 is as catalyst, for the application of electro-catalysis synthesis ammonia, electro-catalysis nitrogen
Gas reduction reaction performance test conditions are same as Example 1, NH3Generating rate is up to 0.86ug/h/cm2, farad at this time
Efficiency is 0.35%.
Embodiment 3:
The preparation of the nitrogen-doped porous carbon material Fe-N/C-600 of metallic iron load, repeats the Fe-N/C-800 material of embodiment 1
Process, the difference is that in step 3) calcining and activating process replacement are as follows: under the conditions of nitrogen protection, from room temperature with 7 DEG C/
The rate of min is warming up to 600 DEG C, then cooled to room temperature after calcining at constant temperature 2 hours again.Remaining step and 1 phase of embodiment
Together, finally obtain iron load nitrogen-doped porous carbon material product (labeled as Fe-N/C-600 material).
Fe-N/C-600 material prepared by embodiment 3 is as catalyst, for the application of electro-catalysis synthesis ammonia, electro-catalysis nitrogen
Gas reduction reaction performance test conditions are same as Example 1, NH3Generating rate is up to 1.05ug/h/cm2, method at this time
Drawing efficiency is 0.38%.
Embodiment 4:
The preparation of the nitrogen-doped porous carbon material Fe-N/C-700 of metallic iron load, repeats the Fe-N/C-800 material of embodiment 1
Process, the difference is that in step 3) calcining and activating process replacement are as follows: under the conditions of nitrogen protection, from room temperature with 7 DEG C/
The rate of min is warming up to 700 DEG C, then cooled to room temperature after calcining at constant temperature 2 hours again.Remaining step and 1 phase of embodiment
Together, finally obtain iron load nitrogen-doped porous carbon material product (labeled as Fe-N/C-700 material).
Fe-N/C-700 material prepared by embodiment 4 is as catalyst, for the application of electro-catalysis synthesis ammonia, electro-catalysis nitrogen
Gas reduction reaction performance test conditions are same as Example 1, NH3Generating rate is up to 1.13ug/h/cm2, method at this time
Drawing efficiency is 0.42%.
Embodiment 5:
The preparation of the nitrogen-doped porous carbon material Fe-N/C-900 of metallic iron load, repeats the Fe-N/C-800 material of embodiment 1
Process, the difference is that in step 3) calcining and activating process replacement are as follows: under the conditions of nitrogen protection, from room temperature with 7 DEG C/
The rate of min is warming up to 900 DEG C, then cooled to room temperature after calcining at constant temperature 2 hours again.Remaining step and 1 phase of embodiment
Together, finally obtain iron load nitrogen-doped porous carbon material product (labeled as Fe-N/C-900 material).
Fe-N/C-900 material prepared by embodiment 5 is as catalyst, for the application of electro-catalysis synthesis ammonia, electro-catalysis nitrogen
Gas reduction reaction performance test conditions are same as Example 1, NH3Generating rate is up to 1.20ug/h/cm2, method at this time
Drawing efficiency is 0.39%.
Embodiment 6:
The preparation of nitrogen-doped porous carbon material N/C repeats the preparation process of embodiment 1, the difference is that, the process of step 1)
Be substituted for: the 2-methylimidazole of 3280mg is dissolved in 50mL methanol, forms solution A；2974mg zinc nitrate hexahydrate is dissolved in
In 50mL methanol, solution B is formed；It is sealed after each leading into nitrogen in solution A and solution B 30 minutes, then by the solution A of sealing
It mixes with solution B, is stored at room temperature 12 hours under air-proof condition.Remaining step is same as Example 1, and it is porous to finally obtain N doping
Carbon material N/C.
N/C material prepared by embodiment 6 is as catalyst, for the application of electro-catalysis synthesis ammonia, the reduction of electro-catalysis nitrogen
Reactivity worth test condition is same as Example 1, and yield and the faradic efficiency result of ammonia are as shown in figure 5, its NH3Generating rate
Up to 0.7ug/h/cm2, faradic efficiency at this time is 0.37%.Comparative example 1 and embodiment 6 are as can be seen that Fe2O3 doping
Improve the electro-catalysis synthesis ammonia activity of material.
Content described in this specification is only to enumerate to inventive concept way of realization, and protection scope of the present invention is not answered
When the concrete form for being seen as limited by embodiment and being stated.
Claims (9)
1. a kind of synthetic method of the iron load nitrogen-doped porous carbon material with excellent electro-catalysis reduction nitrogen performance, feature
It is to include the following steps:
1) imidazoles substance is dissolved in alcohols solvent, forms solution A；Zinc salt and ferrous salt are dissolved in alcohols solvent, formed molten
Liquid B；Nitrogen 30 ~ seal after forty minutes is each led into solution A and solution B, then mixes the solution A of sealing and solution B, it is close
It is stored at room temperature under the conditions of envelope 8 ~ 12 hours；
2) after step 1) is stood, the mixed liquor after standing is placed in a centrifuge centrifuge separation, obtains supernatant and precipitating
Object；By grind into powder after sediment vacuum drying, save backup；
3) powder obtained by step 2 is put into quartz boat, quartz boat, which is placed on again in tube furnace, carries out calcining and activating, obtains black
Color powdered product；
4) black powder product obtained by step 3) is washed with hydrochloric acid solution to remove the zinc in black powder product, then uses deionization
Water washing is removed with the hydrochloric acid that will be adhered on black powder product, then in being dried in vacuum oven to get arriving the iron
Load nitrogen-doped porous carbon material product.
2. a kind of iron with excellent electro-catalysis reduction nitrogen performance as described in claim 1 loads nitrogen-doped porous carbon material
Synthetic method, it is characterised in that in step 1), the imidazoles substance be 2-methylimidazole, the zinc salt be zinc nitrate or chlorine
Change zinc, the ferrous salt is ferrous nitrate or frerrous chloride；The alcohols solvent is methanol or ethyl alcohol, preferably methanol.
3. a kind of iron with excellent electro-catalysis reduction nitrogen performance as described in claim 1 loads nitrogen-doped porous carbon
The synthetic method of material, it is characterised in that in step 1), the amount of the total material of both zinc salt and ferrous salt and the object of imidazoles substance
The ratio between amount of matter is 0.5 ~ 1.5: 4, preferably 1: 4.
4. a kind of iron with excellent electro-catalysis reduction nitrogen performance as described in claim 1 loads nitrogen-doped porous carbon material
Synthetic method, it is characterised in that in step 2, mixed liquor be placed in a centrifuge the revolving speed that is centrifuged be 8000 ~
10000rpm, the time of centrifuge separation are 8 ~ 12 minutes；In step 2, vacuum drying temperature is 60 ~ 80 DEG C, and drying time is
8 ~ 16 hours.
5. a kind of iron with excellent electro-catalysis reduction nitrogen performance as described in claim 1 loads nitrogen-doped porous carbon material
Synthetic method, it is characterised in that in step 3), the process of calcining and activating are as follows: under the conditions of nitrogen protection, from room temperature with 5 ~ 10
DEG C/rate of min is warming up to 500-900 DEG C, then calcining at constant temperature 1 ~ 4 hour again, subsequent cooled to room temperature.
6. a kind of iron with excellent electro-catalysis reduction nitrogen performance as described in claim 1 loads nitrogen-doped porous carbon material
Synthetic method, it is characterised in that in step 4), the concentration of the hydrochloric acid solution is 2 ~ 5mol/L, with hydrochloric acid solution carrying out washing treatment
Time be 6 ~ 8 hours；In step 4), the temperature being dried in vacuum oven is 80 ~ 100 DEG C, and drying time is 8 ~ 16
Hour.
7. iron prepared by the method as described in claim 1 ~ 6 any one loads nitrogen-doped porous carbon material.
8. application of the iron load nitrogen-doped porous carbon material as claimed in claim 7 in electro-catalysis reduction nitrogen synthesis ammonia.
9. application as claimed in claim 8, it is characterised in that the following steps are included:
S1: iron load nitrogen-doped porous carbon material is mixed with the ethanol solution of Nafion, after ultrasonic disperse, by institute's score
Dispersion liquid is dripped on carbon paper, and then carbon paper electrode is made in drying in air；
S2: being to electrode, using acidic aqueous solution as electricity with platinum plate electrode using carbon paper electrode obtained by step S1 as working electrode
Liquid is solved, electrocatalytic reaction is carried out and synthesizes ammonia.
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| CN111346661A (en) * | 2020-03-26 | 2020-06-30 | 浙江理工大学 | Iron-based carbon-nitrogen compound catalytic material for efficiently treating organic wastewater and preparation method thereof |
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| CN113663709A (en) * | 2021-08-20 | 2021-11-19 | 南京师范大学 | Iron-doped carbon material derived from ethyl cellulose and preparation method and application thereof |
| CN113897625A (en) * | 2021-10-14 | 2022-01-07 | 电子科技大学广东电子信息工程研究院 | Composite catalyst and preparation method thereof |
| CN115475641A (en) * | 2022-07-27 | 2022-12-16 | 齐鲁工业大学 | Metal atom anchored boron-nitrogen co-doped carbon material and preparation method thereof |
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| CN111346661A (en) * | 2020-03-26 | 2020-06-30 | 浙江理工大学 | Iron-based carbon-nitrogen compound catalytic material for efficiently treating organic wastewater and preparation method thereof |
| CN113387341A (en) * | 2021-05-26 | 2021-09-14 | 中科院过程工程研究所南京绿色制造产业创新研究院 | Magnetic foam material and preparation method thereof |
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| CN113897625B (en) * | 2021-10-14 | 2022-09-23 | 电子科技大学广东电子信息工程研究院 | Composite catalyst and preparation method thereof |
| CN115475641A (en) * | 2022-07-27 | 2022-12-16 | 齐鲁工业大学 | Metal atom anchored boron-nitrogen co-doped carbon material and preparation method thereof |
| CN115475641B (en) * | 2022-07-27 | 2023-12-22 | 齐鲁工业大学 | Metal atom anchored boron-nitrogen co-doped carbon material and preparation method thereof |
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Application publication date: 20190723 |