CN110055558A - The preparation method and fixed nitrogen method of room temperature fixed nitrogen elctro-catalyst and electro catalytic electrode - Google Patents

The preparation method and fixed nitrogen method of room temperature fixed nitrogen elctro-catalyst and electro catalytic electrode Download PDF

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CN110055558A
CN110055558A CN201910483691.8A CN201910483691A CN110055558A CN 110055558 A CN110055558 A CN 110055558A CN 201910483691 A CN201910483691 A CN 201910483691A CN 110055558 A CN110055558 A CN 110055558A
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fixed nitrogen
electro
coo
room temperature
nitrogen
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CN110055558B (en
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周瑞娟
任学蓉
张平
王平
张超
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NINGXIA HUI AUTONOMOUS REGION ENVIRONMENTAL MONITORING CENTER STATION
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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
    • 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
    • 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
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C25B11/077—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the compound being a non-noble metal oxide

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Abstract

The present invention provides the preparation method and fixed nitrogen method of a kind of Room-temperature low-pressure electro-catalysis fixed nitrogen catalyst and electro catalytic electrode, the catalyst molecule formula is Na0.26CoO2.By Na0.26CoO2, ethylene glycol, nafion solution and distilled water be mixed, ultrasound is coated on graphite paper, and drying obtains Na0.26CoO2Room temperature fixed nitrogen electro catalytic electrode.By Na0.26CoO2Electro-catalysis fixed nitrogen electrode and Hg/HgSO4Electrode assembling is at electro-catalysis fixed nitrogen battery, and in sulfuric acid solution, under -0.1~-1.0V voltage, the nitrogen in atmosphere is catalytically conveted to ammonia.Above-mentioned electro catalytic electrode is in sulfuric acid solution, and under -0.2V voltage, nitrogen atmosphere is catalyzed 1h, NH3Conversion ratio be 31.6ug mg‑1h‑1~39.8ug mg‑1h‑1.The present invention provides new approach for artificial synthesized ammonia for rapid catalytic conversion provides cost-effective method for available ammonia at room temperature using the nitrogen in atmosphere.

Description

The preparation method and fixed nitrogen method of room temperature fixed nitrogen elctro-catalyst and electro catalytic electrode
Technical field
The invention belongs to electro-catalysis nitrogen fixation technology fields, and in particular to a kind of Room-temperature low-pressure electro-catalysis fixed nitrogen catalyst and electricity The preparation method and fixed nitrogen method of catalysis electrode.
Background technique
Nitrogen is the important composition element of the biomolecule such as protein in plant and animal, nucleotide.Although nitrogen molecule (N2) be air main component, but since N ≡ N is highly stable, the higher (940.95kJmol of bond energy-1), it is difficult to it activates.Mesh Before, NH is industrially synthesized by aber process3The condition of high temperature and pressure is needed to activate N2.This exacting terms needs to disappear every year Consume the energy supply of whole world 1-2%.In addition, aber process synthesizes NH3Need hydrogen as one of raw material, and hydrogen main source In the steam reformation of natural gas, this process can discharge a large amount of CO2.In view of the shortage of fossil fuel and the change of global climate Change, exploration synthesizes NH in a mild condition3Catalysis reaction be particularly important.Electrochemical reduction N2Synthesize NH3Reaction is due to can Select natural air as nitrogen source, and reaction can be completed under conditions of low pressure room temperature.Research and development being capable of high-efficiency electrochemical reduction N2Synthesize NH3Elctro-catalyst be a very challenging task.
Summary of the invention
For the above-mentioned prior art, the technical problem to be solved in the present invention is that providing a kind of normal temperature and pressure electro-catalysis nitrogen The method for being converted into the electrocatalysis material and electro catalytic electrode and electro-catalysis fixed nitrogen of ammonia, can complete under conditions of normal pressure and temperature Nitrogen in air is catalytically conveted to ammonia.
The present invention provides a kind of normal temperature and pressure electro-catalysis fixed nitrogen catalyst, the catalyst molecule formula is Na0.26CoO2, Na0.26CoO2Ammonia can be converted into Room-temperature low-pressure electro-catalysis nitrogen.
The present invention also provides a kind of preparation methods of room temperature fixed nitrogen elctro-catalyst, comprising the following steps: will be a certain amount of Co(NO3)2·6H2O and NaNO3It is uniformly mixed, 500 DEG C of holding 2h is warming up to certain rate, then be down to certain rate Room temperature, taking-up are ground into tiny particle, are warming up to 1000 DEG C of holding 12h with certain rate, are cooled to room temperature, adopt after taking-up With chemical removing sodium, it is then centrifuged for separation and dries again, obtain Na0.26CoO2Room temperature fixed nitrogen elctro-catalyst.
Preferably, Co (NO is added3)2·6H2O and NaNO3Molal weight ratio be 0.75:1.
Preferably, heating rate is 10 DEG C/mim, and rate of temperature fall is 10 DEG C/mim.
Preferably, oxide used in chemical removing sodium is the NaClO of saturation4, removing sodium 5 days under stirring.
The present invention also provides a kind of preparation methods of Room-temperature low-pressure electro-catalysis fixed nitrogen electrode, according to a certain ratio will Na0.26CoO2, ethylene glycol, nafion solution and distilled water be mixed, ultrasound is coated on graphite paper, and drying obtains Na0.26CoO2 Nitrogen at room is converted into the electro catalytic electrode of ammonia.
Preferably, the Na0.26CoO2It is prepared by following steps: by a certain amount of Co (NO3)2·6H2O and NaNO3It is mixed It closes uniformly, 500 DEG C of holding 2h is warming up to certain rate, then room temperature is down to certain rate, taking-up is ground into tiny Particle is warming up to 1000 DEG C of holding 12h with certain rate, is cooled to room temperature, and oxide removing sodium is used after taking-up, is then centrifuged for Separation is dried again, obtains Na0.26CoO2Room temperature fixed nitrogen elctro-catalyst.
Preferably, every 20mgNa0.26CoO2Middle addition ethylene glycol 750ul, nafion solution 50ul and distilled water 2ml, it is used Nafion solution mass fraction be 5%.
Preferably, ultrasonic time 10min, drying temperature are 80 DEG C, and drying time is for 24 hours.
The present invention also provides a kind of room temperature electro-catalysis fixed nitrogen methods, by Na0.26CoO2Electro-catalysis fixed nitrogen electrode and Hg/ HgSO4Electrode assembling is at electro-catalysis fixed nitrogen battery, and in sulfuric acid solution, under -0.1~-1.0V voltage, the nitrogen in atmosphere is urged Change is converted into ammonia.
Na prepared by the present invention0.26CoO2Electro-catalysis fixed nitrogen catalyst can be in electro-catalysis under Room-temperature low-pressure by the nitrogen in air Gas is converted into ammonia, has high catalyzed conversion nitrogen fixing capacity.Present invention can apply to prepare Na0.26CoO2The work of electro-catalysis fixed nitrogen Electrode, with Hg/HgSO4It is assembled into electro-catalysis fixed nitrogen battery and is applied to nitrogen in atmosphere and be catalytically conveted to ammonia.For using greatly Rapid catalytic conversion for available ammonia provides cost-effective method at room temperature for nitrogen in gas, while being artificial Synthesis ammonia provides new approach.
Detailed description of the invention
Fig. 1 is Na0.26CoO2Scanning electron microscope (SEM) photograph；
Fig. 2 is Na0.26CoO2XRD diagram；
Fig. 3 is Na0.26CoO2Raman spectrogram；
Fig. 4 is Na0.26CoO2High power transmission electron microscope picture；
Fig. 5 is Na0.26CoO2In sulfuric acid solution, the fixed nitrogen performance test of (- 0.1~-1.0V) under different operating voltage Figure；
Fig. 6 is Na0.26CoO2In sulfuric acid solution, the fixed nitrogen performance map of 10 measurements is recycled；
Fig. 7 is Na0.26CoO2In sulfuric acid solution, the faradic efficiency performance map of 10 measurements is recycled.
Specific embodiment
A specific embodiment of the invention is described in detail with reference to the accompanying drawing:
Embodiment 1:
Na0.26CoO2The preparation of room temperature electro-catalysis fixed nitrogen catalyst: the NaNO for being 0.75:1 by molar ratio3With Co (NO3)2· 6H2O mixing is warming up to 500 DEG C of holding 2h with 10 DEG C/mim, then is down to room temperature with 10 DEG C/mim, and taking-up is ground into tiny Grain is warming up to 1000 DEG C with 10 DEG C/mim, keeps 12h, be cooled to room temperature.Saturation NaClO is put into after taking-up4In solution, stirring 5 It, centrifugation drying is prepared into Na0.26CoO2。
Na0.26CoO2Nitrogen at room is converted into the preparation of the electro catalytic electrode of ammonia: taking the Na of above-mentioned preparation0.26CoO2Electricity Hold desalination electrode material 20mg, ethylene glycol 750ul, 5%nafion solution 50ul, after distilled water 2ml, ultrasonic 10min it is coated On graphite paper, is dried for 24 hours at 80 DEG C, finally obtain Na0.26CoO2 electro catalytic electrode.
Room temperature electro-catalysis fixed nitrogen method, by Na0.26CoO2Electro-catalysis fixed nitrogen electrode and Hg/HgSO4Electrode assembling is at electro-catalysis Nitrogen in atmosphere under -0.1~-1.0V voltage, is catalytically conveted to ammonia in sulfuric acid solution by fixed nitrogen battery.Above-mentioned electricity is urged Polarizing electrode is in sulfuric acid solution, and under -0.2V voltage, nitrogen atmosphere is catalyzed 1h, NH3Conversion ratio be 31.6ugmg-1h-1~ 39.8ugmg-1h-1, faradic efficiency is 8.31%~8.69%.
The embodiments of the present invention are described in detail for above-mentioned combination attached drawing, but the present invention is not limited to above-mentioned implementations Mode can also make many variations to it within the knowledge of one of ordinary skill in the art.

Claims (10)

1. a kind of Room-temperature low-pressure electro-catalysis fixed nitrogen catalyst, which is characterized in that the catalyst molecule formula is Na0.26CoO2。
2. a kind of preparation method of Room-temperature low-pressure electro-catalysis fixed nitrogen catalyst, which comprises the following steps: will be a certain amount of Co (NO3)2·6H2O and NaNO3It is uniformly mixed, 500 DEG C of holding 2h is warming up to certain rate, then drop with certain rate To room temperature, taking-up is ground into tiny particle, is warming up to 1000 DEG C of holding 12h with certain rate, is cooled to room temperature, after taking-up Using chemical removing sodium, it is then centrifuged for separation and dries again, obtain Na0.26CoO2Room temperature fixed nitrogen elctro-catalyst.
3. the preparation method of Room-temperature low-pressure electro-catalysis fixed nitrogen catalyst according to claim 2, which is characterized in that Co is added (NO3)2·6H2O and NaNO3Molal weight ratio be 0.75:1.
4. the preparation method of normal temperature and pressure electro-catalysis fixed nitrogen catalyst according to claim 2, which is characterized in that heating speed Rate is 10 DEG C/mim, and rate of temperature fall is 10 DEG C/mim.
5. the preparation method of Room-temperature low-pressure electro-catalysis fixed nitrogen catalyst according to claim 2, which is characterized in that chemistry is de- Oxide used in sodium is saturation NaClO4Solution, removing sodium 5 days under stirring.
6. a kind of preparation method of Room-temperature low-pressure electro-catalysis fixed nitrogen electrode, which is characterized in that according to a certain ratio by Na0.26CoO2、 Ethylene glycol, nafion solution and distilled water are mixed, ultrasound, coated on graphite paper, and drying obtains Na0.26CoO2Room-temperature low-pressure electricity It is catalyzed fixed nitrogen electrode.
7. the preparation method of Room-temperature low-pressure electro-catalysis fixed nitrogen catalyst electrode according to claim 6, which is characterized in that institute State Na0.26CoO2It is prepared by following steps: according to a certain ratio by Co (NO3)2·6H2O and NaNO3It is uniformly mixed, with certain Rate is warming up to 500 DEG C of holding 2h, then is down to room temperature with certain rate, and taking-up is ground into tiny particle, with certain speed Rate is warming up to 1000 DEG C of holding 12h, is cooled to room temperature, and oxide removing sodium is used after taking-up, is then centrifuged for separation and dries again, obtains Na0.26CoO2Room temperature fixed nitrogen elctro-catalyst.
8. the preparation method of room temperature fixed nitrogen electro catalytic electrode according to claim 6, which is characterized in that sample proportion is every 20mg Na0.26CoO2Middle addition ethylene glycol 750ul, nafion solution 50ul and distilled water 2ml, the matter of nafion solution used Measuring score is 5%.
9. the preparation method of room temperature fixed nitrogen electro catalytic electrode according to claim 6, which is characterized in that ultrasonic time is 10min, drying temperature are 80 DEG C, and drying time is for 24 hours.
10. a kind of room temperature electro-catalysis fixed nitrogen method, which is characterized in that by Na0.26CoO2Electro-catalysis fixed nitrogen electrode and Hg/HgSO4Electricity Pole is assembled into electro-catalysis fixed nitrogen battery, in sulfuric acid solution, under -0.1~-1.0V voltage, by the nitrogen catalyzed conversion in atmosphere For ammonia.
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