CN110055558B - Normal-temperature nitrogen fixing electrocatalyst, preparation method of electrocatalytic electrode and nitrogen fixing method - Google Patents
Normal-temperature nitrogen fixing electrocatalyst, preparation method of electrocatalytic electrode and nitrogen fixing method Download PDFInfo
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- CN110055558B CN110055558B CN201910483691.8A CN201910483691A CN110055558B CN 110055558 B CN110055558 B CN 110055558B CN 201910483691 A CN201910483691 A CN 201910483691A CN 110055558 B CN110055558 B CN 110055558B
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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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
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- 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
Abstract
The invention provides a normal-temperature low-voltage electro-catalysis nitrogen fixation catalyst, a preparation method of an electro-catalysis electrode and a nitrogen fixation method, wherein the molecular formula of the catalyst is Na0.26CoO2. Mixing Na0.26CoO2Mixing with ethylene glycol, nafion solution and distilled water, ultrasonic coating on graphite paper, and oven drying to obtain Na0.26CoO2An electrocatalytic electrode for fixing nitrogen at normal temperature. Mixing Na0.26CoO2Electrocatalytic nitrogen fixation electrode and Hg/HgSO4The electrodes are assembled into an electrocatalytic nitrogen fixation battery, and nitrogen in the atmosphere is catalytically converted into ammonia under the voltage of-0.1 to-1.0V in a sulfuric acid solution. The electrocatalytic electrode catalyzes NH for 1h in a nitrogen atmosphere at-0.2V in a sulfuric acid solution3The conversion rate of (A) was 31.6ug mg‑1h‑1～39.8ug mg‑1h‑1. The invention provides an economic and effective method for rapidly catalyzing and converting nitrogen in the atmosphere into available ammonia at room temperature, and simultaneously provides a new way for artificially synthesizing ammonia.
Description
Technical Field
The invention belongs to the technical field of electrocatalysis nitrogen fixation, and particularly relates to a normal-temperature low-voltage electrocatalysis nitrogen fixation catalyst, a preparation method of an electrocatalysis electrode and a nitrogen fixation method.
Background
Nitrogen is an important constituent element of biomolecules such as proteins and nucleotides in plants and animals. Despite the nitrogen molecule (N)2) Is the main component of air, but has high bonding energy (940.95 kJ. mol.) due to high stability of N ≡ N-1) Activation is difficult. Currently, NH is industrially synthesized by the Haber method3Activation of N under conditions requiring high temperature and high pressure2. Such harsh conditions require 1-2% of the world's energy supply to be consumed each year. Furthermore, the synthesis of NH by the Haber method3Hydrogen is required as one of the feedstocks, and is mainly derived from steam reforming of natural gas, a process which emits large amounts of CO2. In view of the shortage of fossil fuels and the change of global climate, the research is carried outSynthesis of NH under mild conditions3The catalytic reaction is particularly important. Electrochemical reduction of N2Synthesis of NH3The reaction can be completed under the conditions of low pressure and normal temperature because natural air can be selected as a nitrogen source. Research and development of a method capable of efficiently electrochemically reducing N2Synthesis of NH3The electrocatalyst of (a) is a very challenging task.
Disclosure of Invention
In view of the above prior art, the technical problem to be solved by the present invention is to provide an electrocatalytic material and an electrocatalytic electrode for electrocatalytic conversion of nitrogen into ammonia at normal temperature and normal pressure, and a method for electrocatalytic nitrogen fixation, which can complete catalytic conversion of nitrogen in air into ammonia at normal pressure and normal temperature.
The invention provides a normal-temperature normal-pressure electro-catalysis nitrogen fixation catalyst, wherein the molecular formula of the catalyst is Na0.26CoO2，Na0.26CoO2The nitrogen can be electrocatalyzed at normal temperature and low pressure to be converted into ammonia.
The invention also provides a preparation method of the normal-temperature nitrogen-fixing electrocatalyst, which comprises the following steps: a certain amount of Co (NO)3)2·6H2O and NaNO3Mixing, heating to 500 deg.C at a certain rate for 2 hr, cooling to room temperature at a certain rate, taking out, grinding into fine particles, heating to 1000 deg.C at a certain rate for 12 hr, cooling to room temperature, taking out, removing sodium chemically, centrifuging, and oven drying to obtain Na0.26CoO2And (3) fixing nitrogen at normal temperature.
Preferably, Co (NO) is added3)2·6H2O and NaNO3The molar mass ratio of (a) to (b) is 0.75: 1.
Preferably, the temperature increase rate is 10 ℃/mim, and the temperature decrease rate is 10 ℃/mim.
Preferably, the oxide used for chemical sodium removal is saturated NaClO4Sodium was removed under stirring for 5 days.
The invention also provides a preparation method of the normal-temperature low-voltage catalytic nitrogen fixation electrode, which is characterized in that Na is added according to a certain proportion0.26CoO2Mixing with ethylene glycol, nafion solution and distilled waterUltrasonically coating the graphite paper, and drying to obtain Na0.26CoO2An electro-catalysis electrode for converting nitrogen into ammonia at normal temperature.
Preferably, the Na is0.26CoO2Is prepared by the following steps: a certain amount of Co (NO)3)2·6H2O and NaNO3Mixing, heating to 500 deg.C at a certain rate for 2 hr, cooling to room temperature at a certain rate, taking out, grinding into fine particles, heating to 1000 deg.C at a certain rate for 12 hr, cooling to room temperature, removing sodium with oxide, centrifuging, and oven drying to obtain Na0.26CoO2And (3) fixing nitrogen at normal temperature.
Preferably, every 20mgNa0.26CoO2750ul of ethylene glycol, 50ul of nafion solution and 2ml of distilled water are added, and the mass fraction of the nafion solution is 5%.
Preferably, the ultrasonic time is 10min, the drying temperature is 80 ℃, and the drying time is 24 h.
The invention also provides a normal-temperature electrocatalysis nitrogen fixation method, which is to add Na0.26CoO2Electrocatalytic nitrogen fixation electrode and Hg/HgSO4The electrodes are assembled into an electrocatalytic nitrogen fixation battery, and nitrogen in the atmosphere is catalytically converted into ammonia under the voltage of-0.1 to-1.0V in a sulfuric acid solution.
Na produced by the invention0.26CoO2The electro-catalysis nitrogen fixation catalyst can convert nitrogen in the air into ammonia under the condition of electro-catalysis at normal temperature and low pressure, and has high nitrogen fixation catalytic conversion capability. The invention can be applied to the preparation of Na0.26CoO2Electrocatalytic nitrogen fixation working electrode, and Hg/HgSO4The obtained product is assembled into an electrocatalytic nitrogen fixation battery and applied to the catalytic conversion of nitrogen in the atmosphere into ammonia. Provides an economic and effective method for rapidly and catalytically converting nitrogen in the atmosphere into available ammonia at room temperature, and simultaneously provides a new way for artificially synthesizing ammonia.
Drawings
FIG. 1 is Na0.26CoO2Scanning electron microscope images of;
FIG. 2 is Na0.26CoO2XRD pattern of (a);
FIG. 3 is Na0.26CoO2(ii) a Raman spectrogram;
FIG. 4 is Na0.26CoO2High power transmission electron micrographs of;
FIG. 5 is Na0.26CoO2In sulfuric acid solution, nitrogen fixation performance comparison graphs under different working voltages (-0.1 to-1.0V);
FIG. 6 is Na0.26CoO2Circulating the nitrogen fixation performance chart for 10 times of measurement in the sulfuric acid solution;
FIG. 7 is Na0.26CoO2Faraday efficiency performance plots of 10 cycles in sulfuric acid solution.
Detailed Description
The following detailed description of embodiments of the invention refers to the accompanying drawings in which:
example 1:
Na0.26CoO2preparing a normal-temperature electrocatalytic nitrogen fixation catalyst: NaNO with a molar ratio of 0.75:13With Co (NO)3)2·6H2Mixing O, heating to 500 deg.C at 10 deg.C/mim for 2h, cooling to room temperature at 10 deg.C/mim, grinding into fine particles, heating to 1000 deg.C at 10 deg.C/mim, maintaining for 12h, and cooling to room temperature. Taking out and putting in saturated NaClO4Stirring for 5 days in the solution, centrifuging and drying to prepare Na0.26CoO2。
Na0.26CoO2Preparing an electrocatalysis electrode for converting nitrogen into ammonia at normal temperature: collecting Na prepared above0.26CoO220mg of capacitance desalting electrode material, 750ul of ethylene glycol, 50ul of 5% nafion solution and 2ml of distilled water are coated on graphite paper after ultrasonic treatment for 10min, and the graphite paper is dried for 24h at 80 ℃ to finally obtain Na0.26CoO2 electrocatalytic electrode.
The normal temperature electrocatalysis nitrogen fixation method is to add Na0.26CoO2Electrocatalytic nitrogen fixation electrode and Hg/HgSO4The electrodes are assembled into an electrocatalytic nitrogen fixation battery, and nitrogen in the atmosphere is catalytically converted into ammonia gas under the voltage of-0.1 to-1.0V in a sulfuric acid solution. The electrocatalytic electrode is catalyzed in a sulfuric acid solution under-0.2V and nitrogen atmosphere1h，NH3The conversion rate of (A) was 31.6ug mg-1h-1～39.8ugmg-1h-1The Faraday efficiency is 8.31% -8.69%.
The embodiments of the present invention have been described in detail with reference to the drawings, but the present invention is not limited to the embodiments and various changes can be made thereto within the knowledge of those skilled in the art.
Claims (7)
1. A preparation method of a normal-temperature low-voltage electrocatalytic nitrogen fixation catalyst is characterized by comprising the following steps: mixing Co (NO) according to a molar mass ratio of 0.75:13)2·6H2O and NaNO3Mixing, heating to 500 deg.C at a rate of 10 deg.C/min for 2 hr, cooling to room temperature at a rate of 10 deg.C/min, taking out, grinding into fine particles, heating to 1000 deg.C at a certain rate, maintaining for 12 hr, cooling to room temperature, taking out, removing sodium chemically, centrifuging, and oven drying to obtain Na0.26CoO2And (3) fixing nitrogen at normal temperature.
2. The preparation method of normal-temperature low-voltage catalysis nitrogen fixation catalyst as claimed in claim 1, wherein the oxide for chemical sodium removal is saturated NaClO4The solution was sodium-removed under stirring for 5 days.
3. A preparation method of a normal-temperature low-voltage electrocatalytic nitrogen fixation electrode is characterized in that Na is added according to a certain proportion0.26CoO2Mixing with ethylene glycol, nafion solution and distilled water, ultrasonic coating on graphite paper, and oven drying to obtain Na0.26CoO2Normal temperature low voltage electrocatalysis nitrogen fixation electrode, the Na0.26CoO2The normal-temperature nitrogen-fixing electrocatalyst is prepared by the following steps: mixing Co (NO) according to a molar mass ratio of 0.75:13)2·6H2O and NaNO3Mixing, heating to 500 deg.C at a rate of 10 deg.C/min for 2 hr, cooling to room temperature at a rate of 10 deg.C/min, taking out, grinding into fine particles, heating to 1000 deg.C at a certain rate, maintaining for 12 hr,cooling to room temperature, taking out, removing sodium chemically, centrifuging, and oven drying to obtain Na0.26CoO2And (3) fixing nitrogen at normal temperature.
4. The method for preparing the normal-temperature low-voltage electrocatalytic nitrogen fixation electrode as claimed in claim 3, wherein the Na is0.26CoO2Is prepared by the following steps: mixing Co (NO) according to a certain proportion3)2·6H2O and NaNO3Mixing, heating to 500 deg.C at a certain rate for 2 hr, cooling to room temperature at a certain rate, taking out, grinding into fine particles, heating to 1000 deg.C at a certain rate for 12 hr, cooling to room temperature, removing sodium with oxide, centrifuging, and oven drying to obtain Na0.26CoO2And (3) fixing nitrogen at normal temperature.
5. The method for preparing normal-temperature low-voltage electrocatalytic nitrogen fixation electrode as claimed in claim 3, wherein the sample ratio is 20mg Na/g0.26CoO2To this solution, 750. mu.l of ethylene glycol, 50. mu.l of nafion solution and 2ml of distilled water were added, and the nafion solution was used in an amount of 5% by mass.
6. The preparation method of the normal-temperature low-voltage electrocatalytic nitrogen fixation electrode as claimed in claim 3, wherein the ultrasonic time is 10min, the drying temperature is 80 ℃, and the drying time is 24 h.
7. A normal temperature electrocatalytic nitrogen fixation method, characterized in that Na prepared in the claim 30.26CoO2Normal temperature low-voltage electro-catalysis nitrogen fixation electrode and Hg/HgSO4The electrodes are assembled into an electrocatalytic nitrogen fixation battery, and nitrogen in the atmosphere is catalytically converted into ammonia under the voltage of-0.1 to-1.0V in a sulfuric acid solution.
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| US4780381A (en) * | 1987-11-05 | 1988-10-25 | Allied-Signal, Inc. | Rechargeable battery cathode from sodium cobalt dioxide in the O3, O'3, P3 and/or P'3 phases |
| JP2001029944A (en) * | 1999-07-26 | 2001-02-06 | Shimadzu Corp | Method for removing nitrogen compound in water |
| JP2003206138A (en) * | 2002-01-09 | 2003-07-22 | Sk Kaken Co Ltd | Cobalt-containing compound oxide having brucite type crystal structure |
| CN102784647A (en) * | 2012-08-14 | 2012-11-21 | 浙江大学 | Preparation method for (101)-surface nanoFe-TiO2 high-efficiency nitrogen-fixing photocatalyst |
| CN104415758A (en) * | 2013-09-06 | 2015-03-18 | 中国科学院大连化学物理研究所 | Preparation method and applications of non-noble metal electrocatalyst |
| CN103866343B (en) * | 2014-03-25 | 2017-01-11 | 内蒙古科技大学 | Method and device for synthesizing ammonia through carrying out efficient electrocatalytic reduction on nitrogen gas at low temperature and normal pressure |
| IS2972B (en) * | 2014-06-13 | 2017-07-15 | Háskóli Íslands | Process and system for electrolytic production of ammonia |
| CN107262117B (en) * | 2017-07-25 | 2020-06-19 | 华中师范大学 | Single-atom metal-doped few-layer molybdenum disulfide electrocatalytic material, synthesis method and electrocatalytic nitrogen fixation method thereof |
| CN107999114A (en) * | 2017-12-19 | 2018-05-08 | 成都玖奇新材料科技有限公司 | Electrochemical reduction nitrogen ammonia non-precious metal catalyst |
| CN109775764B (en) * | 2019-01-10 | 2021-03-23 | 三峡大学 | Spherical NaxCoO2Sodium ion battery positive electrode material and preparation method thereof |
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| CN109647407A (en) * | 2019-02-12 | 2019-04-19 | 济南大学 | A kind of preparation method and application based on bimetallic MOF nanocrystalline composite material |
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