WO2021077730A1 - Nitrogen fixation device and method using low-temperature jet flow plasma coupled with monatomic catalysis - Google Patents
Nitrogen fixation device and method using low-temperature jet flow plasma coupled with monatomic catalysis Download PDFInfo
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- WO2021077730A1 WO2021077730A1 PCT/CN2020/090746 CN2020090746W WO2021077730A1 WO 2021077730 A1 WO2021077730 A1 WO 2021077730A1 CN 2020090746 W CN2020090746 W CN 2020090746W WO 2021077730 A1 WO2021077730 A1 WO 2021077730A1
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- the invention belongs to the technical fields of low-temperature jet plasma activation catalysis and single-atom catalysts in the synthesis of ammonia and energy storage, and particularly relates to a method that uses low-temperature jet plasma to activate air, nitrogen, and water, and couples single-atom electrocatalysis to achieve online/offline distributed Technical methods for the synthesis of ammonia, nitric acid, nitrogen oxides and other chemicals.
- Nitrogen fixation refers to the conversion of abundant nitrogen molecules in the atmosphere into nitrogen-containing compounds (such as ammonia, nitrate, nitrogen dioxide, etc.). It is one of the most basic biochemical reactions in nature, maintaining the global nitrogen cycle and the survival of plants and animals. .
- the free nitrogen in nature has a stable electronic structure (N ⁇ N,948kJ/mol), which is difficult to be used directly. It can only fix nitrogen through the nitrogen fixation of a few microorganisms and the high-energy action of lightning.
- the population explosion and the rapid development of industry and agriculture in the past 100 years have sharply spawned the demand for nitrogen fixation, thus driving the continuous innovation of artificial nitrogen fixation technology.
- the mainstream industrial nitrogen fixation technology is still the Haber process developed in the last century.
- the electrochemically catalyzed nitrogen reduction (NRR) ammonia synthesis technology is inspired by the participation of protons and electrons in biological enzymes in the nitrogen fixation reaction. It uses cheap nitrogen (air) and water as raw materials.
- the electrode voltage can be flexibly controlled to achieve normal temperature and pressure. Nitrogen fixation has gradually become a research hotspot in the field of nitrogen fixation.
- electrocatalytic ammonia synthesis technology is more flexible and convenient, and can be compatible with local renewable energy sources (including intermittent energy such as wind, solar, and tidal energy) according to local conditions
- local renewable energy sources including intermittent energy such as wind, solar, and tidal energy
- Plasma is divided into high-temperature plasma and low-temperature plasma.
- Low-temperature plasma generally refers to plasma with a macroscopic temperature below 100,000K.
- Low-temperature plasma technology is well compatible with new energy sources such as solar energy and wind energy, and can be efficiently activated under normal temperature and pressure conditions.
- Nitrogen molecules in the air realize nitrogen fixation.
- Low-temperature plasma as another potential nitrogen fixation technology, can rely on vibrationally excited nitrogen molecules, free radicals and other active nitrogen-containing ions to significantly optimize the catalytic environment and interaction mechanism on the electrocatalyst surface, reduce the N 2 activation energy, and strengthen Single atom electrocatalytic nitrogen fixation effect.
- the low-temperature plasma can react with the electrocatalytic nitrogen fixation by-products hydrogen, water, etc., to form activated water rich in reactive nitrogen, oxygen and other components as a new type of electrolyte, and use ammonia, nitric acid and ammonium nitrate (NH 3 +HNO 3 ⁇ NH 4 NO 3 ) realizes secondary nitrogen fixation, which improves the overall economy of the system.
- the purpose of the present invention is to solve the problems of low ammonia yield, poor selectivity, and high comprehensive cost in the existing electrocatalytic nitrogen fixation process in order to solve the problems of low ammonia yield, poor selectivity and high comprehensive cost in the existing electrocatalytic nitrogen fixation process.
- Jet plasma technology activates air, nitrogen and water to produce active electrolyte, and then single-atom catalytic active electrolyte is reduced to produce synthetic ammonia.
- This method has the advantages of simple process, high disposal efficiency, wide application range, flexible adjustability, high product value and high product value. Good compatibility with renewable energy.
- a low-temperature jet plasma coupled single-atom catalyzed nitrogen fixation device which includes an electrochemical workstation, a plasma power supply, an H-type electrolytic cell and a jet plasma reactor;
- the electrochemical workstation includes a reference electrode clamp, a working electrode clamp, and a counter electrode clamp;
- the plasma power supply includes a power supply positive electrode and a power supply negative electrode;
- the H-type electrolytic cell includes a first argon gas inlet, a first argon gas outlet, a proton exchange membrane, a second argon gas inlet, and a second argon gas outlet; the reference electrode and electrochemical cell of the H-type electrolytic cell
- the reference electrode clamp in the workstation is connected, the working electrode of the H-type electrolytic cell is connected with the working electrode clamp in the electrochemical workstation, and the counter electrode of the H-type electrolytic cell is connected with the counter electrode in the electrochemical workstation.
- the jet plasma reactor includes an inner electrode, an outer electrode, and a gas channel.
- the inner electrode is connected to the positive electrode of the plasma power source, and the outer electrode is connected to the negative electrode of the plasma power source.
- the gas channel is used for communication. Enter the gas to discharge the jet plasma in the jet plasma reactor;
- the proton exchange membrane is between the two H-type electrolytic cells to prevent gas diffusion from affecting the progress of the positive and negative reactions.
- a low-temperature jet plasma coupled single-atom catalysis nitrogen fixation method is an off-line operation mode and includes the following steps:
- the precursor of the transition metal catalyst is calcined at a high temperature in a tube furnace at a calcination temperature of 800 degrees, and ammonia gas is introduced into the tube furnace to prepare the transition metal monoatomic catalyst.
- the precursor of the transition metal catalyst includes Cu, Fe, Ni, Co metal particles grown on a carbon substrate;
- step (2) After mixing the transition metal monoatomic catalyst prepared in step (1), the naphthol solution with a mass fraction of 5% and anhydrous ethanol, brush on carbon paper and dry to obtain the working electrode of the H-type electrolytic cell , Wherein the volume ratio of naphthol solution and absolute ethanol is 7:10000, and the loading amount of transition metal monoatomic catalyst is 0.57mg/cm 2 ⁇ 0.86mg/cm 2 ;
- the CV stabilizes the current and performs an electrochemical catalysis process at different applied voltages (1.1V-1.6V) for 30 minutes, and collects the reacted NH 4 + solution in the H-type electrolytic cell.
- the nitrogen fixation method is an online operation mode; in the online operation mode, the jet plasma reactor is fixed in the H-type electrolytic cell, and the discharge end directly reacts with the solution in the H-type electrolytic cell; H- After the working electrode of the type electrolytic cell, adjust the parameters to be consistent with the offline operation, and turn on the plasma power supply and electrochemical workstation at the same time, and perform denutrition.
- the oxygen removal method is consistent with offline operation.
- the working time of the plasma power supply and electrochemical workstation In addition, the voltage applied by the electrochemical workstation is consistent with the offline operation to realize the ammonia synthesis reaction, and collect the NH 4 + -containing solution after the reaction in the H-type electrolytic cell.
- the gas products of the H-type electrolytic cell are collected, and the concentration of the gaseous nitrogen fixation products produced is analyzed and tested by gas chromatography;
- the value of the product is high; compared with the traditional ammonia synthesis reaction, the present invention can also produce high concentration nitrogen oxides based on plasma activation, which can also be used as a chemical product through collection; in addition, there is high purity oxygen at the anode of the electrolytic cell Produced are all conducive to improving the overall economy.
- each reaction parameter under this method including plasma discharge power, gas flow, electrode applied potential, etc., can be flexibly adjusted. It can achieve the target results by flexibly changing the operating conditions for different components, different disposal amounts, target products and other conditions.
- the design of the device is reasonable; the device integrates the characteristics of a jet low-temperature plasma reaction device and an electrochemical electrolysis device, and combines the advantages of high power density of plasma equipment, strong processing capacity, strong selectivity of electrochemical equipment, and high product purity. The advantages of low energy consumption, easy control, flexible adjustment, and outstanding effects.
- Figure 1 is a diagram of an apparatus for coupling monoatomic electrocatalytic nitrogen fixation using low-temperature plasma jets in offline mode
- Figure 2 is a diagram of an apparatus for coupling monoatomic electrocatalytic nitrogen fixation using low-temperature plasma jets in online mode
- Figure 3 is the standard curve of the experiment for calculating the yield of synthetic ammonia
- Electrochemical platform 2. Plasma power supply; 3. Reference electrode; 4. Working electrode; 5. Counter electrode; 6. H-type electrolytic cell; 7. First argon inlet; 8. Section An argon outlet; 9. Proton exchange membrane; 10. The second argon inlet; 11. The second argon outlet; 12. Power supply positive electrode; 13. Power supply negative electrode; 14. Jet plasma reactor.
- the invention utilizes the principle of low-temperature plasma jet coupling single-atom electrocatalytic nitrogen fixation.
- the jet low-temperature plasma generates abundant ions, electrons, active molecules, free radicals, etc., which can activate molecules such as air, nitrogen, water, and oxygen, and pass them
- the collision and dissociation between them breaks chemical bonds such as OO, H-OH, NN, etc., forming raw materials required for electrocatalysis.
- the active electrolyte formed by the plasma will be converted into synthetic ammonia.
- a low-temperature jet plasma coupled single-atom catalysis nitrogen fixation device the device includes an electrochemical workstation 1, a plasma power source 2, an H-type electrolytic cell 6 and a jet plasma reactor 14;
- the electrochemical workstation 1 includes a reference electrode clamp 3, a working electrode clamp 4, and a counter electrode clamp 5;
- the plasma power source 2 includes a power supply positive electrode 12 and a power supply negative electrode 13;
- the H-shaped electrolytic cell 6 includes a first argon gas inlet 7, a first argon gas outlet 8, a proton exchange membrane 9, a second argon gas inlet 10, and a second argon gas outlet 11; the H-shaped electrolytic cell 6
- the reference electrode is connected to the reference electrode clamp 3 in the electrochemical workstation 1
- the working electrode of the H-type electrolytic cell 6 is connected to the working electrode clamp 4 in the electrochemical workstation 1
- the counter electrode of the cell 6 is connected with the counter electrode clamp 5 in the electrochemical workstation 1 to form a loop of the electrocatalytic process;
- the jet plasma reactor 14 includes an inner electrode, an outer electrode, and a gas channel.
- the inner electrode is connected to the positive electrode 12 of the plasma power source 2 and the outer electrode is connected to the negative electrode 13 of the plasma power source 2;
- the gas channel is used to pass in gas to discharge the jet plasma in the jet plasma reactor 14;
- the proton exchange membrane 9 is between the two H-type electrolytic cells 6 to prevent gas diffusion from affecting the progress of the positive and negative reactions.
- a low-temperature jet plasma coupled single-atom catalysis nitrogen fixation method is an off-line operation mode, and includes the following steps:
- the precursor of the transition metal catalyst is calcined at a high temperature in a tube furnace at a calcination temperature of 800 degrees, and ammonia gas is introduced into the tube furnace to prepare the transition metal monoatomic catalyst.
- the precursor of the transition metal catalyst includes Cu, Fe, Ni, Co metal particles grown on a carbon substrate;
- step (2) After mixing the transition metal monoatom catalyst prepared in step (1), the naphthol solution with a mass fraction of 5% and absolute ethanol, brush on carbon paper and dry to obtain the work of the H-type electrolytic cell 6 An electrode, wherein the volume ratio of the naphthol solution and the absolute ethanol is 7:10000, and the loading amount of the transition metal monoatomic catalyst is 0.57 mg/cm 2 to 0.86 mg/cm 2 ;
- the CV stabilizes the current, and the electrochemical catalysis process is carried out at different applied voltages (1.1V-1.6V) for 30 minutes to collect the reacted NH 4 + solution in the H-type electrolytic cell 6 .
- a low-temperature jet plasma coupled single atom catalysis nitrogen fixation method also has an online operation mode; in the online operation mode, the jet plasma reactor 14 is fixed in the H-type electrolytic cell 6, and the discharge end Directly react with the solution in the H-type electrolytic cell 6; after the working electrode of the H-type electrolytic cell 6 is prepared, and adjust the parameters to be consistent with the offline operation, turn on the plasma power supply 2 and electrochemical workstation 1 at the same time, and perform the removal
- the maintenance and removal methods are the same as offline operation.
- the working hours of plasma power supply 2 and electrochemical workstation 1 and the voltage applied by electrochemical workstation 1 are consistent with offline operation to realize the synthesis of ammonia reaction and collect the H-type electrolytic cell 6
- the reacted solution contains NH 4 +.
- the obtained powder was placed in a crucible and heated to 650° C. at a heating rate of 5° C./min under an argon atmosphere and kept for four hours to obtain a monoatomic Mo catalyst SA-Mo/NPC.
- the monoatomic Mo catalyst SA-Mo/NPC was painted on a carbon cloth as a working electrode for the electrocatalytic reaction of nitrogen fixation, and the resulting synthetic ammonia yield was 34 ⁇ g/h.
- a tube furnace is used to calcinate the precursor of the transition metal catalyst at a high temperature with a calcining temperature of 800 degrees, and ammonia gas is introduced into the tube furnace to prepare a Co monoatomic catalyst.
- the prepared Co single-atom catalyst with a load of 0.7 mg/cm 2 , 0.7 ⁇ L of DuPont D520 (5% wt) nafion solution and 1 mL of absolute ethanol were dropped on the carbon paper and dried to prepare an H-type electrolytic cell 6 Working electrode;
- the reaction solution After half an hour of reaction, the reaction solution is absorbed 4ml and the indophenol blue developer After mixing and standing for 2 hours, the standard curve of synthetic ammonia yield calculated according to the experiment shown in Figure 3 (the abscissa is x represents the concentration of NH 4 + , the ordinate is y represents the absorbance, and R is the linear correlation of the fitted curve °C), use an ultraviolet spectrophotometer to detect the concentration of NH 4 + in the reaction solution.
- a tube furnace is used to calcinate the precursor of the transition metal catalyst at a high temperature with a calcining temperature of 800 degrees, and ammonia gas is introduced into the tube furnace to prepare a Co monoatomic catalyst.
- the prepared Co single-atom catalyst with a load of 0.7 mg/cm 2 , 0.7 ⁇ L of DuPont D520 (5% wt) nafion solution and 1 mL of absolute ethanol were dropped on the carbon paper and dried to prepare an H-type electrolytic cell 6 Working electrode;
- the reaction solution After half an hour of reaction, the reaction solution is absorbed 4ml and the indophenol blue developer After mixing and standing for 2 hours, the standard curve of synthetic ammonia yield calculated according to the experiment shown in Figure 3 (the abscissa is x represents the concentration of NH 4 + , the ordinate is y represents the absorbance, and R is the linear correlation of the fitted curve °C), use an ultraviolet spectrophotometer to detect the concentration of NH 4 + in the reaction solution.
- the effect is best when the gas flow rate is 7L/min. This result is mainly because the gas flow rate will affect the discharge effect of the plasma reactor. A larger gas flow rate will push the plasma arc outwards, thus The area of the discharge area is increased, and when the gas flow is further increased, the gas will take away a large amount of energy, and the area of the discharge area will be reduced, so that the discharge effect will be reduced.
- a tube furnace is used to calcinate the precursor of the transition metal catalyst at a high temperature with a calcining temperature of 800 degrees, and ammonia gas is introduced into the tube furnace to prepare a Co monoatomic catalyst.
- the prepared Co single-atom catalyst with a load of 0.7 mg/cm 2 , 0.7 ⁇ L of DuPont D520 (5% wt) nafion solution and 1 mL of absolute ethanol were dropped on the carbon paper and dried to prepare an H-type electrolytic cell 6 Working electrode;
- the reaction solution After half an hour of reaction, the reaction solution is absorbed 4ml and the indophenol blue developer After mixing and standing for 2 hours, the standard curve of synthetic ammonia yield calculated according to the experiment shown in Figure 3 (the abscissa is x represents the concentration of NH 4 + , the ordinate is y represents the absorbance, and R is the linear correlation of the fitted curve °C), use an ultraviolet spectrophotometer to detect the concentration of NH 4 + in the reaction solution.
- the yield of synthetic ammonia is higher. This is because oxygen can increase the concentration of nitrite in the solution after the reaction.
- the source of nitrogen in synthetic ammonia is mainly nitrite. .
- a tubular furnace is used to calcinate the precursor of the transition metal catalyst at a high temperature with a calcination temperature of 800 degrees, and ammonia gas is introduced into the tubular furnace to prepare different transition metal monoatomic catalysts.
- the prepared Cu different loading 0.7mg / cm 2 of, Fe, Ni, Co monatomic catalyst, 0.7 ⁇ L DuPont D520 (5% wt) nafion solution dropwise 1mL of anhydrous ethanol in carbon paper, and drying to obtain Working electrode of H-type electrolytic cell 6;
- the reaction solution After half an hour of reaction, the reaction solution is absorbed 4ml and the indophenol blue developer After mixing and standing for 2 hours, according to the standard curve calculated for the synthetic ammonia yield in the experiment shown in Figure 3 (the abscissa is the concentration of NH 4 + , the ordinate is the absorbance), the NH 4 + in the reaction solution is detected by an ultraviolet spectrophotometer. concentration.
- a tube furnace is used to calcinate the precursor of the transition metal catalyst at a high temperature with a calcining temperature of 800 degrees, and ammonia gas is introduced into the tube furnace to prepare a Co monoatomic catalyst.
- the prepared Co single-atom catalysts with different loadings of 0.7 mg/cm 2 , 0.7 ⁇ L of DuPont D520 (5% wt) nafion solution and 1 mL of absolute ethanol were dropped on the carbon paper and dried to prepare an H-type electrolytic cell 6 Working electrode;
- a tube furnace is used to calcinate the precursor of the transition metal catalyst at a high temperature with a calcining temperature of 800 degrees, and ammonia gas is introduced into the tube furnace to prepare a Co monoatomic catalyst.
- Different loading produced 0.57mg / cm 2, 0.7mg / cm 2, 0.86mg / cm Co monoatomic catalyst 2, 0.7 ⁇ L DuPont D520 (5% wt) nafion solution and 1mL of anhydrous ethanol dropwise carbon paper
- the working electrode of the H-shaped electrolytic cell 6 is obtained by drying;
- the reaction solution After half an hour of reaction, the reaction solution is absorbed 4ml and the indophenol blue developer After mixing and standing for 2 hours, the standard curve of synthetic ammonia yield calculated according to the experiment shown in Figure 3 (the abscissa is x represents the concentration of NH 4 + , the ordinate is y represents the absorbance, and R is the linear correlation of the fitted curve °C), use an ultraviolet spectrophotometer to detect the concentration of NH 4 + in the reaction solution.
- the yield of obtained synthetic ammonia is much higher than the existing conventional yield of synthetic ammonia obtained by electrocatalysis.
- a tube furnace is used to calcinate the precursor of the transition metal catalyst at a high temperature with a calcining temperature of 800 degrees, and ammonia gas is introduced into the tube furnace to prepare a Co monoatomic catalyst.
- the prepared Co single-atom catalysts with different loadings of 0.7 mg/cm 2 , 0.7 ⁇ L of DuPont D520 (5% wt) nafion solution and 1 mL of absolute ethanol were dropped on the carbon paper and dried to prepare an H-type electrolytic cell 6 Working electrode;
- the electrochemical workstation At the same time as the plasma discharge reaction starts, turn on the electrochemical workstation to remove the prepared working electrode and chlorine.
- the silver electrode and the platinum sheet electrode are respectively connected to the working electrode holder 4, the reference electrode holder 3 and the counter electrode holder 5 of the electrochemical workstation 1.
- a voltage of 1.3V is applied to carry out the electrochemical catalytic reaction.
- 4 ml of the reaction solution was absorbed and mixed with the indophenol blue developer, and after standing for 2 hours, the NH 4 + concentration in the reaction solution was detected by an ultraviolet spectrophotometer.
- This mode is an online detection mode. Compared with the offline mode, this method can continuously provide nitrogen-containing substances by treating the liquid surface for a long time. At the same time, the two devices of the H-type electrolytic cell and the jet plasma reactor are combined in Together, the operation is more convenient and the control is more flexible.
- the method of the present invention while ammonia, along with the oxidation product prepared nitrogenase NO x, and nitric acid.
- the two treatment processes of coupling low-temperature plasma and single-atom catalyst not only ensure the high-efficiency activation of nitrogen, but also ensure the selectivity of ammonia synthesis, and realize high-efficiency economy based on the production of oxidized nitrogen fixation products.
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Abstract
Disclosed are a nitrogen fixation device and method using low-temperature jet flow plasma coupled with monatomic catalysis. The nitrogen fixation device comprises an electrochemical workstation, a plasma power supply, an H-type electrolytic cell and a jet flow plasma reactor. The method involves firstly preparing a transition metal monatomic catalyst, and thus preparing a working electrode of the H-type electrolytic cell; directly introducing air, nitrogen, or a mixed gas of oxygen and nitrogen into the jet flow plasma reactor, turning on the plasma power supply to achieve a stable discharge of jet flow plasma, and after the jet flow plasma reactor is discharged for 10 minutes, turning off the plasma power supply; and transferring the reaction liquid after discharge into the H-type electrolytic cell, finally turning on the electrochemical workstation to perform an electrochemical catalytic process for 30 min, and collecting a solution containing NH4
+ after the reaction in the H-type electrolytic cell. The present invention is high in efficiency and environmentally friendly, and combines plasma discharge and an electrochemical catalytic reaction, wherein a monatomic catalyst is beneficial to the improvement of the yield and reaction rate of ammonia synthesis.
Description
本发明属于低温射流等离子活化催化和单原子催化剂在合成氨及储能等技术领域,尤其涉及一种采用低温射流等离子体活化空气、氮气及水,并耦合单原子电催化实现在线/离线的分布式合成氨、合成硝酸、氮氧化物等化学品的技术方法。The invention belongs to the technical fields of low-temperature jet plasma activation catalysis and single-atom catalysts in the synthesis of ammonia and energy storage, and particularly relates to a method that uses low-temperature jet plasma to activate air, nitrogen, and water, and couples single-atom electrocatalysis to achieve online/offline distributed Technical methods for the synthesis of ammonia, nitric acid, nitrogen oxides and other chemicals.
固氮,指将大气中储量丰富的氮分子转化成含氮化合物(如氨、硝酸盐、二氧化氮等),是自然界最基础的生化反应之一,维系着全球氮循环和动植物生存所需。自然界中的游离态氮电子结构稳定(N≡N,948kJ/mol),很难被直接利用,仅可通过少数微生物的固氮作用和闪电的高能作用固氮。然而,近百年来的人口爆炸和工农业的迅猛发展,急剧催生了固氮需求,从而驱动了人工固氮技术的不断革新。目前,主流的工业固氮技术仍为发展于上世纪的哈柏法
约占人工固氮总量的40%;其以氨形式固定的氮元素被广泛应用于农牧、化工和制药等行业,满足了全球40%人口的氮需求。但该技术以高纯氢为原料,需严苛的催化条件(450~600℃,148~350atm)实现固氮,巨大的能源消耗和严重的环境污染使其饱受争议。据统计,哈柏法直接消耗了全球近1~2%的能源和近3~5%的天然气,同时排放了近3亿吨的CO2(约占全球CO2排放总量的3%),其生产过程中产生的大量高氨氮、可生化性差的废水,更是极难处置。因此,在能源环境问题日益凸显及氮需求急剧增加的今天,发展可替代的低碳、高效、清洁的新型人工固氮技术迫在眉睫。电化学催化氮还原(NRR)的合成氨技术来源于生物酶中质子和电子参与固氮反应的启发,以廉价的氮气(空气)和水作为原料,可通过电极电压的灵活控制,实现常温常压下的固氮,逐渐成为当今固氮领域的研究热点。相比设施工艺复杂、反应条件严苛、能耗污染巨大的哈柏法,电催化合成氨技术更灵活、便捷,可因地制宜地兼容当地可再生能源(包括风能、太阳能和潮汐能等间歇性能源)的电力供给,实现小型化、分布式的新型固氮理念,为偏远落后地区或不具备合成氨工业应用基础的发展中国家提供清洁的固氮保障。
Nitrogen fixation refers to the conversion of abundant nitrogen molecules in the atmosphere into nitrogen-containing compounds (such as ammonia, nitrate, nitrogen dioxide, etc.). It is one of the most basic biochemical reactions in nature, maintaining the global nitrogen cycle and the survival of plants and animals. . The free nitrogen in nature has a stable electronic structure (N≡N,948kJ/mol), which is difficult to be used directly. It can only fix nitrogen through the nitrogen fixation of a few microorganisms and the high-energy action of lightning. However, the population explosion and the rapid development of industry and agriculture in the past 100 years have sharply spawned the demand for nitrogen fixation, thus driving the continuous innovation of artificial nitrogen fixation technology. At present, the mainstream industrial nitrogen fixation technology is still the Haber process developed in the last century. It accounts for about 40% of the total amount of artificial nitrogen fixation; its nitrogen fixed in the form of ammonia is widely used in agriculture, animal husbandry, chemical and pharmaceutical industries, and meets the nitrogen demand of 40% of the world's population. However, this technology uses high-purity hydrogen as a raw material, and requires harsh catalytic conditions (450-600°C, 148-350 atm) to achieve nitrogen fixation. The huge energy consumption and serious environmental pollution have caused it to be controversial. According to statistics, the Haber process directly consumes nearly 1 to 2% of the world’s energy and nearly 3 to 5% of natural gas, and emits nearly 300 million tons of CO2 (about 3% of the total global CO2 emissions). The large amount of wastewater with high ammonia nitrogen and poor biodegradability produced in the process is extremely difficult to dispose of. Therefore, with the increasingly prominent energy and environmental issues and the rapid increase in nitrogen demand today, the development of alternative low-carbon, high-efficiency, and clean new artificial nitrogen fixation technologies is urgently needed. The electrochemically catalyzed nitrogen reduction (NRR) ammonia synthesis technology is inspired by the participation of protons and electrons in biological enzymes in the nitrogen fixation reaction. It uses cheap nitrogen (air) and water as raw materials. The electrode voltage can be flexibly controlled to achieve normal temperature and pressure. Nitrogen fixation has gradually become a research hotspot in the field of nitrogen fixation. Compared with the Haber process, which has complex facilities, severe reaction conditions, and huge energy consumption pollution, electrocatalytic ammonia synthesis technology is more flexible and convenient, and can be compatible with local renewable energy sources (including intermittent energy such as wind, solar, and tidal energy) according to local conditions The power supply to realize the miniaturization and distributed new nitrogen fixation concept, to provide clean nitrogen fixation guarantee for remote and backward areas or developing countries that do not have the basis for the application of synthetic ammonia industry.
目前,仅少数过渡金属、过渡金属氧化物、碳材料及酶催化剂等被应用于合成氨反应研究,但效果均不理想。近年发展提出“单原子催化剂”,凭借“孤立活性位点”、“不饱和配位环境”和“100%金属原子利用率”等特点,已在电解水、燃料电池、CO
2还原等诸多领域取得了显著地成果,因此可为固氮领域提供新的高效电催化提供新的选择,但常规水溶液体系中的析氢电位和氮还原电位非常接近,析氢作为竞争反应会严重影响电催化合成氨的效率, 也是制约电催化固氮产业化的关键技术难点。等离子体分为高温等离子和低温等离子,低温等离子一般指宏观温度在100000K以下的等离子体,低温等离子技术能够很好地兼容太阳能、风能等新能源,同时又能够在常温、常压条件下高效活化空气中的氮气分子,实现固氮。低温等离子体作为另一潜在固氮技术,可凭借着振动激发态的氮分子、自由基及其他活性含氮离子,显著优化电催化剂表面的催化环境及与互作用机制,降低N
2活化能,强化单原子电催化固氮效果。同时,低温等离子可与电催化的固氮副产物氢气、水等反应,形成富含活性氮、氧等成分的活化水作为新型电解液,并以氨、硝酸和硝酸铵(NH
3+HNO
3→NH
4NO
3)等形式实现二次固氮,提升了体系的整体经济性。
At present, only a few transition metals, transition metal oxides, carbon materials and enzyme catalysts have been used in the research of ammonia synthesis reaction, but the effect is not satisfactory. In recent years, the development of "single-atom catalysts" has been proposed. With the characteristics of "isolated active sites", "unsaturated coordination environment" and "100% metal atom utilization", it has been used in many fields such as electrolysis of water, fuel cells, CO 2 reduction, etc. Significant results have been achieved, so it can provide new options for the field of nitrogen fixation with new high-efficiency electrocatalysis. However, the hydrogen evolution potential and nitrogen reduction potential in conventional aqueous systems are very close. Hydrogen evolution as a competitive reaction will seriously affect the efficiency of electrocatalytic ammonia synthesis. It is also a key technical difficulty that restricts the industrialization of electrocatalytic nitrogen fixation. Plasma is divided into high-temperature plasma and low-temperature plasma. Low-temperature plasma generally refers to plasma with a macroscopic temperature below 100,000K. Low-temperature plasma technology is well compatible with new energy sources such as solar energy and wind energy, and can be efficiently activated under normal temperature and pressure conditions. Nitrogen molecules in the air realize nitrogen fixation. Low-temperature plasma, as another potential nitrogen fixation technology, can rely on vibrationally excited nitrogen molecules, free radicals and other active nitrogen-containing ions to significantly optimize the catalytic environment and interaction mechanism on the electrocatalyst surface, reduce the N 2 activation energy, and strengthen Single atom electrocatalytic nitrogen fixation effect. At the same time, the low-temperature plasma can react with the electrocatalytic nitrogen fixation by-products hydrogen, water, etc., to form activated water rich in reactive nitrogen, oxygen and other components as a new type of electrolyte, and use ammonia, nitric acid and ammonium nitrate (NH 3 +HNO 3 → NH 4 NO 3 ) realizes secondary nitrogen fixation, which improves the overall economy of the system.
因此,基于电催化固氮反应体系(涵盖电催化剂、电解液及相应的电子质子传递和离子扩散等过程)的全局考虑,创新性地开发基于低温等离子体协同单原子电催化耦合系统和设备并应用于固氮,可破解传统电催化产率低,活化难等难题,最终实现高效、清洁、分布式的绿色固氮,提高新型固氮整体的经济和社会效益。Therefore, based on the overall consideration of the electrocatalytic nitrogen fixation reaction system (covering electrocatalysts, electrolytes, and corresponding electronic proton transfer and ion diffusion processes), innovatively develop and apply low-temperature plasma-based synergistic single-atom electrocatalytic coupling systems and equipment For nitrogen fixation, it can solve the problems of low yield of traditional electrocatalysis and difficult activation, and finally realize efficient, clean, distributed green nitrogen fixation, and improve the overall economic and social benefits of the new type of nitrogen fixation.
发明内容Summary of the invention
本发明目的在于针对现有技术的不足,提出一种低温射流等离子体耦合单原子催化的固氮方法,解决现有电催化固氮过程中氨产率低、选择性差、综合成本过高等问题,利用低温射流等离子技术活化空气、氮气和水,产生的活性电解液,而后单原子催化活性电解液还原生成合成氨,该方法具有工艺简单、处置效率高、适用范围广、可调性灵活、产物价值高并与可再生能源良好兼容等特点。The purpose of the present invention is to solve the problems of low ammonia yield, poor selectivity, and high comprehensive cost in the existing electrocatalytic nitrogen fixation process in order to solve the problems of low ammonia yield, poor selectivity and high comprehensive cost in the existing electrocatalytic nitrogen fixation process. Jet plasma technology activates air, nitrogen and water to produce active electrolyte, and then single-atom catalytic active electrolyte is reduced to produce synthetic ammonia. This method has the advantages of simple process, high disposal efficiency, wide application range, flexible adjustability, high product value and high product value. Good compatibility with renewable energy.
本发明的目的是通过以下技术方案来实现的:一种低温射流等离子体耦合单原子催化的固氮装置,该装置包括电化学工作站、等离子体电源、H-型电解池和射流等离子体反应器;The purpose of the present invention is achieved through the following technical solutions: a low-temperature jet plasma coupled single-atom catalyzed nitrogen fixation device, which includes an electrochemical workstation, a plasma power supply, an H-type electrolytic cell and a jet plasma reactor;
所述电化学工作站包括参比电极夹、工作电极夹和对电极夹;所述等离子体电源包括电源正极和电源负极;The electrochemical workstation includes a reference electrode clamp, a working electrode clamp, and a counter electrode clamp; the plasma power supply includes a power supply positive electrode and a power supply negative electrode;
所述H-型电解池包括第一氩气进口、第一氩气出口、质子交换膜、第二氩气进口和第二氩气出口;所述H-型电解池的参比电极与电化学工作站中的参比电极夹相连接,所述H-型电解池的工作电极与电化学工作站中的工作电极夹相连接,所述H-型电解池的对电极与电化学工作站中的对电极夹相连接,形成电催化过程的回路;The H-type electrolytic cell includes a first argon gas inlet, a first argon gas outlet, a proton exchange membrane, a second argon gas inlet, and a second argon gas outlet; the reference electrode and electrochemical cell of the H-type electrolytic cell The reference electrode clamp in the workstation is connected, the working electrode of the H-type electrolytic cell is connected with the working electrode clamp in the electrochemical workstation, and the counter electrode of the H-type electrolytic cell is connected with the counter electrode in the electrochemical workstation. Clip phase connection to form a loop of electrocatalytic process;
所述射流等离子体反应器包括內电极、外电极和气体通道,所述内电极与等离子体电源的电源正极连接,所述外电极与等离子体电源的电源负极连接;所述气体通道用于通入气体,使射流等离子体反应器中的射流等离子体放电;The jet plasma reactor includes an inner electrode, an outer electrode, and a gas channel. The inner electrode is connected to the positive electrode of the plasma power source, and the outer electrode is connected to the negative electrode of the plasma power source. The gas channel is used for communication. Enter the gas to discharge the jet plasma in the jet plasma reactor;
所述质子交换膜在两个H-型电解池之间,防止因气体扩散而影响正负极反应的进行。The proton exchange membrane is between the two H-type electrolytic cells to prevent gas diffusion from affecting the progress of the positive and negative reactions.
一种低温射流等离子体耦合单原子催化的固氮方法,该固氮方法为离线运行模式,包括 以下步骤:A low-temperature jet plasma coupled single-atom catalysis nitrogen fixation method. The nitrogen fixation method is an off-line operation mode and includes the following steps:
(1)利用管式炉高温煅烧过渡金属催化剂的前驱物,煅烧温度为800度,并向管式炉中通入氨气,制备过渡金属单原子催化剂。所述过渡金属催化剂的前驱物包括生长在炭基底上的Cu、Fe、Ni、Co的金属粒子;(1) The precursor of the transition metal catalyst is calcined at a high temperature in a tube furnace at a calcination temperature of 800 degrees, and ammonia gas is introduced into the tube furnace to prepare the transition metal monoatomic catalyst. The precursor of the transition metal catalyst includes Cu, Fe, Ni, Co metal particles grown on a carbon substrate;
(2)将步骤(1)制备的过渡金属单原子催化剂、质量分数为5%的萘酚溶液和无水乙醇混合后,刷在碳纸上,烘干制得H-型电解池的工作电极,其中,萘酚溶液和无水乙醇的体积比为7:10000,过渡金属单原子催化剂的负载量为0.57mg/cm
2~0.86mg/cm
2;
(2) After mixing the transition metal monoatomic catalyst prepared in step (1), the naphthol solution with a mass fraction of 5% and anhydrous ethanol, brush on carbon paper and dry to obtain the working electrode of the H-type electrolytic cell , Wherein the volume ratio of naphthol solution and absolute ethanol is 7:10000, and the loading amount of transition metal monoatomic catalyst is 0.57mg/cm 2 ~0.86mg/cm 2 ;
(3)将空气、氮气或者氧气和氮气混合气体直接通入射流等离子体反应器;并利用质量流量计调节进入射流等离子体反应器的气体的流量和比例,所述氧气和氮气混合气体中氧气和氮气的体积比为4:6~1:9;调节气体流量为4L/min~8L/min;打开等离子体电源,利用等离子体电源调节输入射流等离子体反应器两端的功率,实现射流等离子体稳定的放电,调节射流等离子体反应器的放电端与反应容器中的液面距离在1cm-5cm之间;射流等离子体反应器放电10分钟后,关闭等离子体电源;(3) Directly pass air, nitrogen or a mixed gas of oxygen and nitrogen into the incident flow plasma reactor; and use a mass flow meter to adjust the flow rate and proportion of the gas entering the jet plasma reactor. The oxygen in the oxygen and nitrogen mixed gas is The volume ratio with nitrogen is 4:6~1:9; the gas flow rate is adjusted to 4L/min~8L/min; the plasma power is turned on, and the plasma power is used to adjust the power input to both ends of the jet plasma reactor to achieve jet plasma Stable discharge, adjust the distance between the discharge end of the jet plasma reactor and the liquid surface in the reaction vessel between 1cm-5cm; turn off the plasma power supply after 10 minutes of discharge in the jet plasma reactor;
(4)向H型电解池的两个反应池中分别移入50ml放电之后的反应液,同时经过第一氩气进口和第二氩气进口向H-型电解池中的电解液中通入氩气,实现除氧;氩气从第一氩气出口和第二氩气出口流出;(4) Transfer 50ml of the reaction solution after discharge into the two reaction cells of the H-shaped electrolytic cell, and pass argon into the electrolyte in the H-shaped electrolytic cell through the first argon inlet and the second argon inlet at the same time Argon gas to achieve deoxygenation; argon gas flows out from the first argon gas outlet and the second argon gas outlet;
(5)开启电化学工作站后CV稳定电流后在不同的施加电压(1.1V-1.6V)下进行30min电化学催化过程,收集H-型电解池中的反应后的含有NH
4
+溶液。
(5) After the electrochemical workstation is turned on, the CV stabilizes the current and performs an electrochemical catalysis process at different applied voltages (1.1V-1.6V) for 30 minutes, and collects the reacted NH 4 + solution in the H-type electrolytic cell.
进一步地,该固氮方法为在线运行模式;所述在线运行模式中,射流等离子体反应器固定在H-型电解池中,放电端与H-型电解池中的溶液直接反应;制得H-型电解池的工作电极后,并调节参数与离线运行时一致,同时打开等离子体电源和电化学工作站,并进行除养,除氧方式与离线运行一致,等离子体电源和电化学工作站的工作时间还有电化学工作站施加的电压与离线运行保持一致,实现合成氨反应,收集H-型电解池中的反应后的含有NH
4
+溶液。
Further, the nitrogen fixation method is an online operation mode; in the online operation mode, the jet plasma reactor is fixed in the H-type electrolytic cell, and the discharge end directly reacts with the solution in the H-type electrolytic cell; H- After the working electrode of the type electrolytic cell, adjust the parameters to be consistent with the offline operation, and turn on the plasma power supply and electrochemical workstation at the same time, and perform denutrition. The oxygen removal method is consistent with offline operation. The working time of the plasma power supply and electrochemical workstation In addition, the voltage applied by the electrochemical workstation is consistent with the offline operation to realize the ammonia synthesis reaction, and collect the NH 4 + -containing solution after the reaction in the H-type electrolytic cell.
进一步地,运行过程中,收集H-型电解池的气体产物,并用气相色谱分析测试产生的气态固氮产物的浓度;Further, during the operation, the gas products of the H-type electrolytic cell are collected, and the concentration of the gaseous nitrogen fixation products produced is analyzed and tested by gas chromatography;
进一步地,取4ml在H-型电解池中反应后的含有NH
4
+溶液,加入靛酚蓝显色溶液后静置两小时后得到不同深度的绿色溶液;利用紫外-分光光度计测试得到的溶液,获得合成氨的产率。
Further, take 4 ml of the NH 4 + solution after reaction in the H-type electrolytic cell, add the indophenol blue coloring solution and let it stand for two hours to obtain green solutions of different depths; the results are obtained by UV-spectrophotometer test Solution, obtain the yield of synthetic ammonia.
本发明的有益效果:The beneficial effects of the present invention:
(1)效率高;利用低温等离子体能量密度高和能量分布均匀的特点,能有效地将空气、 氮气和氧气等活化,打断对应的化学键,形成较为简单的自由基,为后续的电化学催化合成氨提供所需的原料。单原子催化剂,具有高效的催化利用率和选择性,有利于提升合成氨的产率和反应速率。(1) High efficiency; using the characteristics of high energy density and uniform energy distribution of low-temperature plasma, it can effectively activate air, nitrogen, and oxygen, break the corresponding chemical bonds, and form relatively simple free radicals, which can be used for subsequent electrochemistry. Catalytic synthesis of ammonia provides required raw materials. The single-atom catalyst has high catalytic utilization and selectivity, which is beneficial to increase the yield and reaction rate of synthetic ammonia.
(2)产物价值高;相比较于传统合成氨反应,本发明中基于等离子体活化还可以产生高浓度氮氧化物,通过收集也可作为化学用品;此外,在电解池的阳极有高纯的氧气产生,均有利于提升整体的经济性。(2) The value of the product is high; compared with the traditional ammonia synthesis reaction, the present invention can also produce high concentration nitrogen oxides based on plasma activation, which can also be used as a chemical product through collection; in addition, there is high purity oxygen at the anode of the electrolytic cell Produced are all conducive to improving the overall economy.
(3)环境友好;电化学和等离子放电相结合的模式,提供了非常高的能量密度,其产物主要以含氮化合物为主,都具有较高的利用价值,且整体系统与传统的哈伯法合成氨相比,绿色环保;无二氧化碳等温室气体排出。(3) Environmentally friendly; the combined mode of electrochemistry and plasma discharge provides a very high energy density, and its products are mainly nitrogen-containing compounds, all of which have high utility value, and the overall system is comparable to the traditional Hubble Compared with synthetic ammonia, it is green and environmentally friendly; there is no emission of carbon dioxide and other greenhouse gases.
(4)可调性强;该方法下各个反应参数,包括等离子放电功率、气流量、电极施加电位等,均可实现灵活调节。可以实现针对不同组分、不同处置量、目标产物等条件,灵活改变运行工况得到目标结果。(4) Strong tunability; each reaction parameter under this method, including plasma discharge power, gas flow, electrode applied potential, etc., can be flexibly adjusted. It can achieve the target results by flexibly changing the operating conditions for different components, different disposal amounts, target products and other conditions.
(5)装置设计合理;该装置整合了射流低温等离子反应装置和电化学电解装置的特点,兼具了等离子设备功率密度高,处理能力强的优点以及电化学设备选择性强,产物纯度高,能耗小的优点,易于控制,调节灵活,效果突出。(5) The design of the device is reasonable; the device integrates the characteristics of a jet low-temperature plasma reaction device and an electrochemical electrolysis device, and combines the advantages of high power density of plasma equipment, strong processing capacity, strong selectivity of electrochemical equipment, and high product purity. The advantages of low energy consumption, easy control, flexible adjustment, and outstanding effects.
图1是离线模式下利用低温等离子体射流耦合单原子电催化固氮的装置图;Figure 1 is a diagram of an apparatus for coupling monoatomic electrocatalytic nitrogen fixation using low-temperature plasma jets in offline mode;
图2是在线模式下利用低温等离子体射流耦合单原子电催化固氮的装置图;Figure 2 is a diagram of an apparatus for coupling monoatomic electrocatalytic nitrogen fixation using low-temperature plasma jets in online mode;
图3是实验对于合成氨产率计算的标准曲线;Figure 3 is the standard curve of the experiment for calculating the yield of synthetic ammonia;
图中:1.电化学平台;2.等离子体电源;3.参比电极;4.工作电极;5.对电极;6.H-型电解池;7.第一氩气进口;8.第一氩气出口;9.质子交换膜;10.第二氩气进口;11.第二氩气出口;12.电源正电极;13.电源负极;14.射流等离子体反应器。In the figure: 1. Electrochemical platform; 2. Plasma power supply; 3. Reference electrode; 4. Working electrode; 5. Counter electrode; 6. H-type electrolytic cell; 7. First argon inlet; 8. Section An argon outlet; 9. Proton exchange membrane; 10. The second argon inlet; 11. The second argon outlet; 12. Power supply positive electrode; 13. Power supply negative electrode; 14. Jet plasma reactor.
以下结合附图对本发明具体实施方式作进一步详细说明。The specific embodiments of the present invention will be described in further detail below with reference to the accompanying drawings.
本发明利用低温等离子体射流耦合单原子电催化固氮原理,主要是射流低温等离子体产生丰富的离子、电子、活跃分子、自由基等,能够活化空气、氮气、水和氧气等分子,并通过它们之间的碰撞和解离作用,断裂O-O,H-OH,N-N等化学键,形成电催化所需要的原料。在电化学平台施加的电位区间内,等离子体形成的活性电解液会转化成合成氨。The invention utilizes the principle of low-temperature plasma jet coupling single-atom electrocatalytic nitrogen fixation. The jet low-temperature plasma generates abundant ions, electrons, active molecules, free radicals, etc., which can activate molecules such as air, nitrogen, water, and oxygen, and pass them The collision and dissociation between them breaks chemical bonds such as OO, H-OH, NN, etc., forming raw materials required for electrocatalysis. In the potential range applied by the electrochemical platform, the active electrolyte formed by the plasma will be converted into synthetic ammonia.
如图1所示,一种低温射流等离子体耦合单原子催化的固氮装置,该装置包括电化学工作站1、等离子体电源2、H-型电解池6和射流等离子体反应器14;As shown in Figure 1, a low-temperature jet plasma coupled single-atom catalysis nitrogen fixation device, the device includes an electrochemical workstation 1, a plasma power source 2, an H-type electrolytic cell 6 and a jet plasma reactor 14;
所述电化学工作站1包括参比电极夹3、工作电极夹4和对电极夹5;所述等离子体电源 2包括电源正极12和电源负极13;The electrochemical workstation 1 includes a reference electrode clamp 3, a working electrode clamp 4, and a counter electrode clamp 5; the plasma power source 2 includes a power supply positive electrode 12 and a power supply negative electrode 13;
所述H-型电解池6包括第一氩气进口7、第一氩气出口8、质子交换膜9、第二氩气进口10和第二氩气出口11;所述H-型电解池6的参比电极与电化学工作站1中的参比电极夹3相连接,所述H-型电解池6的工作电极与电化学工作站1中的工作电极夹4相连接,所述H-型电解池6的对电极与电化学工作站1中的对电极夹5相连接,形成电催化过程的回路;The H-shaped electrolytic cell 6 includes a first argon gas inlet 7, a first argon gas outlet 8, a proton exchange membrane 9, a second argon gas inlet 10, and a second argon gas outlet 11; the H-shaped electrolytic cell 6 The reference electrode is connected to the reference electrode clamp 3 in the electrochemical workstation 1, the working electrode of the H-type electrolytic cell 6 is connected to the working electrode clamp 4 in the electrochemical workstation 1, and the H-type electrolytic cell The counter electrode of the cell 6 is connected with the counter electrode clamp 5 in the electrochemical workstation 1 to form a loop of the electrocatalytic process;
所述射流等离子体反应器14包括內电极、外电极和气体通道,所述内电极与等离子体电源2的电源正极12连接,所述外电极与等离子体电源2的电源负极13连接;所述气体通道用于通入气体,使射流等离子体反应器14中的射流等离子体放电;The jet plasma reactor 14 includes an inner electrode, an outer electrode, and a gas channel. The inner electrode is connected to the positive electrode 12 of the plasma power source 2 and the outer electrode is connected to the negative electrode 13 of the plasma power source 2; The gas channel is used to pass in gas to discharge the jet plasma in the jet plasma reactor 14;
所述质子交换膜9在两个H-型电解池6之间,防止因气体扩散而影响正负极反应的进行。The proton exchange membrane 9 is between the two H-type electrolytic cells 6 to prevent gas diffusion from affecting the progress of the positive and negative reactions.
一种低温射流等离子体耦合单原子催化的固氮方法,该固氮方法为离线运行模式,包括以下步骤:A low-temperature jet plasma coupled single-atom catalysis nitrogen fixation method, the nitrogen fixation method is an off-line operation mode, and includes the following steps:
(1)利用管式炉高温煅烧过渡金属催化剂的前驱物,煅烧温度为800度,并向管式炉中通入氨气,制备过渡金属单原子催化剂。所述过渡金属催化剂的前驱物包括生长在炭基底上的Cu、Fe、Ni、Co的金属粒子;(1) The precursor of the transition metal catalyst is calcined at a high temperature in a tube furnace at a calcination temperature of 800 degrees, and ammonia gas is introduced into the tube furnace to prepare the transition metal monoatomic catalyst. The precursor of the transition metal catalyst includes Cu, Fe, Ni, Co metal particles grown on a carbon substrate;
(2)将步骤(1)制备的过渡金属单原子催化剂、质量分数为5%的萘酚溶液和无水乙醇混合后,刷在碳纸上,烘干制得H-型电解池6的工作电极,其中,萘酚溶液和无水乙醇的体积比为7:10000,过渡金属单原子催化剂的负载量为0.57mg/cm
2~0.86mg/cm
2;
(2) After mixing the transition metal monoatom catalyst prepared in step (1), the naphthol solution with a mass fraction of 5% and absolute ethanol, brush on carbon paper and dry to obtain the work of the H-type electrolytic cell 6 An electrode, wherein the volume ratio of the naphthol solution and the absolute ethanol is 7:10000, and the loading amount of the transition metal monoatomic catalyst is 0.57 mg/cm 2 to 0.86 mg/cm 2 ;
(3)将空气、氮气或者氧气和氮气混合气体直接通入射流等离子体反应器14;并利用质量流量计调节进入射流等离子体反应器14的气体的流量和比例,所述氧气和氮气混合气体中氧气和氮气的体积比为4:6~1:9;调节气体流量为4L/min~8L/min;打开等离子体电源2,利用等离子体电源2调节输入射流等离子体反应器14两端的功率,实现射流等离子体稳定的放电,调节射流等离子体反应器14的放电端与反应容器中的液面距离在1cm-5cm之间;射流等离子体反应器14放电10分钟后,关闭等离子体电源2;(3) Directly pass air, nitrogen, or a mixed gas of oxygen and nitrogen into the incident flow plasma reactor 14; and use a mass flow meter to adjust the flow rate and proportion of the gas entering the jet plasma reactor 14. The oxygen and nitrogen mixed gas The volume ratio of oxygen and nitrogen is 4:6~1:9; the gas flow rate is adjusted to 4L/min~8L/min; the plasma power supply 2 is turned on, and the plasma power supply 2 is used to adjust the power input to both ends of the jet plasma reactor 14 , To realize the stable discharge of the jet plasma, adjust the distance between the discharge end of the jet plasma reactor 14 and the liquid surface in the reaction vessel between 1cm-5cm; after the jet plasma reactor 14 discharges for 10 minutes, turn off the plasma power supply 2 ;
(4)向H型电解池6的两个反应池中分别移入50ml放电之后的反应液,同时经过第一氩气进口7和第二氩气进口10向H-型电解池6中的电解液中通入氩气,实现除氧;氩气从第一氩气出口8和第二氩气出口11流出;(4) Transfer 50ml of the reaction solution after discharge into the two reaction cells of the H-shaped electrolytic cell 6, and at the same time pass through the first argon gas inlet 7 and the second argon gas inlet 10 to the electrolyte in the H-shaped electrolytic cell 6 Argon gas is passed through to achieve deoxygenation; argon gas flows out from the first argon gas outlet 8 and the second argon gas outlet 11;
(5)开启电化学工作站1后CV稳定电流后在不同的施加电压(1.1V-1.6V)下进行30min电化学催化过程,收集H-型电解池6中的反应后的含有NH
4
+溶液。
(5) After the electrochemical workstation 1 is turned on, the CV stabilizes the current, and the electrochemical catalysis process is carried out at different applied voltages (1.1V-1.6V) for 30 minutes to collect the reacted NH 4 + solution in the H-type electrolytic cell 6 .
如图2所示,一种低温射流等离子体耦合单原子催化的固氮方法还具有在线运行模式;所述在线运行模式中,射流等离子体反应器14固定在H-型电解池6中,放电端与H-型电解池6中的溶液直接反应;制得H-型电解池6的工作电极后,并调节参数与离线运行时一致, 同时打开等离子体电源2和电化学工作站1,并进行除养,除养方式与离线运行一致,等离子体电源2和电化学工作站1的工作时间还有电化学工作站1施加的电压与离线运行保持一致,实现合成氨反应,收集H-型电解池6中的反应后的含有NH
4
+溶液。
As shown in Figure 2, a low-temperature jet plasma coupled single atom catalysis nitrogen fixation method also has an online operation mode; in the online operation mode, the jet plasma reactor 14 is fixed in the H-type electrolytic cell 6, and the discharge end Directly react with the solution in the H-type electrolytic cell 6; after the working electrode of the H-type electrolytic cell 6 is prepared, and adjust the parameters to be consistent with the offline operation, turn on the plasma power supply 2 and electrochemical workstation 1 at the same time, and perform the removal The maintenance and removal methods are the same as offline operation. The working hours of plasma power supply 2 and electrochemical workstation 1 and the voltage applied by electrochemical workstation 1 are consistent with offline operation to realize the synthesis of ammonia reaction and collect the H-type electrolytic cell 6 The reacted solution contains NH 4 +.
在离线或者在线运行过程中,收集H-型电解池6的气体产物,并用气相色谱分析测试产生的气态固氮产物的浓度;During offline or online operation, collect the gas products of the H-type electrolytic cell 6, and use gas chromatography to analyze and test the concentration of the gaseous nitrogen fixation products produced;
取4ml在H-型电解池6中反应后的含有NH
4
+溶液,加入靛酚蓝显色溶液后静置两小时后得到不同深度的绿色溶液;利用紫外-分光光度计测试得到的溶液,获得合成氨的产率。
Take 4ml of the NH 4 + solution after the reaction in the H-type electrolytic cell 6, add the indophenol blue coloring solution and let it stand for two hours to obtain green solutions of different depths; use the UV-spectrophotometer to test the obtained solution, The yield of synthetic ammonia is obtained.
已有的通过制备单原子催化剂,进行电催化得到合成氨的方法中,所得的合成氨产率非常小,本发明的方法可大幅度提高电催化合成氨的产率,以下给出一个对比例以及本发明的实施例。In the existing methods for obtaining synthetic ammonia through electrocatalysis by preparing a single-atom catalyst, the resulting synthetic ammonia yield is very small. The method of the present invention can greatly increase the yield of electrocatalytic ammonia synthesis. A comparative example and the present invention are given below.的实施例。 Example.
对比例1Comparative example 1
首先将144mg的葡萄糖(C6H12O6)溶解在40ml的无水乙醇中,然后再将40ml的金属盐溶液,包括7.75mg钼酸铵((NH4)6Mo7O24)和690mg盐酸羟胺((NH3OH)Cl),逐滴加入到之前的混合溶液中,之后在70℃的温度下搅拌16h,使溶液中的酒精和水分蒸发,将最终形成的产物研磨成粉末。First dissolve 144mg of glucose (C6H12O6) in 40ml of absolute ethanol, then 40ml of metal salt solution, including 7.75mg of ammonium molybdate ((NH4)6Mo7O24) and 690mg of hydroxylamine hydrochloride ((NH3OH)Cl), Add dropwise to the previous mixed solution, then stir at 70°C for 16 hours to evaporate the alcohol and water in the solution, and grind the final product into a powder.
然后将所得粉末置于坩埚中在氩气氛围下以5℃/min的升温速率加热至650℃并保持四小时从而得到单原子Mo催化剂SA-Mo/NPC。Then, the obtained powder was placed in a crucible and heated to 650° C. at a heating rate of 5° C./min under an argon atmosphere and kept for four hours to obtain a monoatomic Mo catalyst SA-Mo/NPC.
最后将单原子Mo催化剂SA-Mo/NPC涂刷在碳布上作为工作电极进行固氮的电催化反应,所得合成氨产率为34μg/h。Finally, the monoatomic Mo catalyst SA-Mo/NPC was painted on a carbon cloth as a working electrode for the electrocatalytic reaction of nitrogen fixation, and the resulting synthetic ammonia yield was 34 μg/h.
实施例1-5Example 1-5
利用管式炉采用高温煅烧过渡金属催化剂的前驱物,煅烧温度范围800度,并向管式炉中通入氨气,制备Co单原子催化剂。将制备的负载量为0.7mg/cm
2的Co单原子催化剂、0.7μL的杜邦D520(5%wt)nafion溶液和1mL无水乙醇滴在碳纸上,烘干制得H-型电解池6的工作电极;
A tube furnace is used to calcinate the precursor of the transition metal catalyst at a high temperature with a calcining temperature of 800 degrees, and ammonia gas is introduced into the tube furnace to prepare a Co monoatomic catalyst. The prepared Co single-atom catalyst with a load of 0.7 mg/cm 2 , 0.7 μL of DuPont D520 (5% wt) nafion solution and 1 mL of absolute ethanol were dropped on the carbon paper and dried to prepare an H-type electrolytic cell 6 Working electrode;
取160ml的0.1M KOH到反应容器中,将反应容器置于磁力搅拌机上,转速设为240rpm,分别调整射流等离子反应器14放电端与反应容器中反应液面的距离至1、2、3、4、5cm,将等离子体电源2的电源正极12和电源负极13与射流等离子体反应器14连接,向射流等离子反应器14通入空气并通过质量流量控制计将流量调整到7L/min,开启等离子体电源2,调整电压到10KV,即发生等离子液面放电反应,反应时间为10min;Take 160ml of 0.1M KOH into the reaction vessel, place the reaction vessel on a magnetic stirrer, set the speed to 240rpm, and adjust the distance between the discharge end of the jet plasma reactor 14 and the reaction liquid surface in the reaction vessel to 1, 2, 3, 4, 5cm, connect the positive pole 12 of the plasma power supply 2 and the negative pole 13 of the power supply to the jet plasma reactor 14, pass air into the jet plasma reactor 14, and adjust the flow to 7L/min through the mass flow controller, and turn it on Plasma power supply 2, adjust the voltage to 10KV, that is, plasma liquid surface discharge reaction occurs, and the reaction time is 10min;
待反应结束后,向H-型电解池6的两个反应池中分别移入50ml放电后的反应液;将所制得的工作电极、氯化银电极和铂片电极分别与电化学工作站1的工作电极夹4、参比电极夹3以及对电极夹5相连接,在CV稳定回路电流之后施加1.3V电压进行电化学催化反应,反应半小时之后将反应液吸取4ml与靛酚蓝显色剂混合,静置2小时后,根据图3所示的实验对于合成氨产率计算的标准曲线(横坐标为x表示NH
4
+浓度,纵坐标为y表示吸光度,R为该拟合曲线的线性相关度),用紫外分光光度计检测反应液中NH
4
+浓度。
After the reaction is over, transfer 50ml of the discharged reaction solution into the two reaction cells of the H-type electrolytic cell 6 respectively; combine the prepared working electrode, silver chloride electrode and platinum electrode with the electrochemical workstation 1 The working electrode clamp 4, the reference electrode clamp 3 and the counter electrode clamp 5 are connected. After the CV stabilizes the loop current, a voltage of 1.3V is applied for electrochemical catalytic reaction. After half an hour of reaction, the reaction solution is absorbed 4ml and the indophenol blue developer After mixing and standing for 2 hours, the standard curve of synthetic ammonia yield calculated according to the experiment shown in Figure 3 (the abscissa is x represents the concentration of NH 4 + , the ordinate is y represents the absorbance, and R is the linear correlation of the fitted curve ℃), use an ultraviolet spectrophotometer to detect the concentration of NH 4 + in the reaction solution.
下表为不同放电距离的反应效果对比数据:The following table shows the comparison data of the response effect of different discharge distances:
由实施例结果可知,放电距离越小,对液体表面的处理越彻底,进而得到的产率越高。即使放电距离为5cm,所得的合成氨产率也是接近对比例中的两倍。It can be seen from the results of the examples that the smaller the discharge distance, the more thorough the treatment of the liquid surface, and the higher the yield. Even if the discharge distance is 5 cm, the resulting synthetic ammonia yield is close to twice that of the comparative example.
实施例6-10Example 6-10
利用管式炉采用高温煅烧过渡金属催化剂的前驱物,煅烧温度范围800度,并向管式炉中通入氨气,制备Co单原子催化剂。将制备的负载量为0.7mg/cm
2的Co单原子催化剂、0.7μL的杜邦D520(5%wt)nafion溶液和1mL无水乙醇滴在碳纸上,烘干制得H-型电解池6的工作电极;
A tube furnace is used to calcinate the precursor of the transition metal catalyst at a high temperature with a calcining temperature of 800 degrees, and ammonia gas is introduced into the tube furnace to prepare a Co monoatomic catalyst. The prepared Co single-atom catalyst with a load of 0.7 mg/cm 2 , 0.7 μL of DuPont D520 (5% wt) nafion solution and 1 mL of absolute ethanol were dropped on the carbon paper and dried to prepare an H-type electrolytic cell 6 Working electrode;
取160ml的0.1M KOH到反应容器中,将反应容器置于磁力搅拌机上,转速设为240rpm,调整射流等离子反应器14放电端与反应容器中反应液面的距离至1cm,将等离子体电源2的电源正极12和电源负极13与射流等离子体反应器14连接,向射流等离子反应器14通入空气并通过质量流量控制计分别将流量调整到4、5、6、7、8L/min,开启等离子体电源2,调整电压到10KV,即发生等离子液面放电反应,反应时间为10min;Take 160ml of 0.1M KOH into the reaction vessel, place the reaction vessel on a magnetic stirrer, set the speed to 240rpm, adjust the distance between the discharge end of the jet plasma reactor 14 and the reaction liquid surface in the reaction vessel to 1cm, and set the plasma power supply 2 The positive pole 12 of the power supply and the negative pole 13 of the power supply 13 are connected to the jet plasma reactor 14, and air is introduced into the jet plasma reactor 14 and the flow is adjusted to 4, 5, 6, 7, 8 L/min through the mass flow control meter, and then turned on. Plasma power supply 2, adjust the voltage to 10KV, that is, plasma liquid surface discharge reaction occurs, and the reaction time is 10min;
待反应结束后,向H-型电解池6的两个反应池中分别移入50ml放电后的反应液;将所制得的工作电极、氯化银电极和铂片电极分别与电化学工作站1的工作电极夹4、参比电极夹3以及对电极夹5相连接,在CV稳定回路电流之后施加1.3V电压进行电化学催化反应,反应半小时之后将反应液吸取4ml与靛酚蓝显色剂混合,静置2小时后,根据图3所示的实验对于合成氨产率计算的标准曲线(横坐标为x表示NH
4
+浓度,纵坐标为y表示吸光度,R为该拟合曲线的线性相关度),用紫外分光光度计检测反应液中NH
4
+浓度。
After the reaction is over, transfer 50ml of the discharged reaction solution into the two reaction cells of the H-type electrolytic cell 6 respectively; combine the prepared working electrode, silver chloride electrode and platinum electrode with the electrochemical workstation 1 The working electrode clamp 4, the reference electrode clamp 3 and the counter electrode clamp 5 are connected. After the CV stabilizes the loop current, a voltage of 1.3V is applied for electrochemical catalytic reaction. After half an hour of reaction, the reaction solution is absorbed 4ml and the indophenol blue developer After mixing and standing for 2 hours, the standard curve of synthetic ammonia yield calculated according to the experiment shown in Figure 3 (the abscissa is x represents the concentration of NH 4 + , the ordinate is y represents the absorbance, and R is the linear correlation of the fitted curve ℃), use an ultraviolet spectrophotometer to detect the concentration of NH 4 + in the reaction solution.
下表为不同气流量的反应效果对比数据:The following table shows the comparison data of the reaction effect of different air flow rates:
由实施例结果可知,在气流量为7L/min时效果最佳,该结果主要是由于气流量会对等离子反应器的放电效果产生影响,较大的气流量会将等离子弧向外推移,从而增大了放电区域的面积,而当气流量进一步提高后,气体会带走大量的能量,放电区域面积会减小,从而放电效果会降低。It can be seen from the results of the examples that the effect is best when the gas flow rate is 7L/min. This result is mainly because the gas flow rate will affect the discharge effect of the plasma reactor. A larger gas flow rate will push the plasma arc outwards, thus The area of the discharge area is increased, and when the gas flow is further increased, the gas will take away a large amount of energy, and the area of the discharge area will be reduced, so that the discharge effect will be reduced.
实施例11-15Examples 11-15
利用管式炉采用高温煅烧过渡金属催化剂的前驱物,煅烧温度范围800度,并向管式炉中通入氨气,制备Co单原子催化剂。将制备的负载量为0.7mg/cm
2的Co单原子催化剂、0.7μL的杜邦D520(5%wt)nafion溶液和1mL无水乙醇滴在碳纸上,烘干制得H-型电解池6的工作电极;
A tube furnace is used to calcinate the precursor of the transition metal catalyst at a high temperature with a calcining temperature of 800 degrees, and ammonia gas is introduced into the tube furnace to prepare a Co monoatomic catalyst. The prepared Co single-atom catalyst with a load of 0.7 mg/cm 2 , 0.7 μL of DuPont D520 (5% wt) nafion solution and 1 mL of absolute ethanol were dropped on the carbon paper and dried to prepare an H-type electrolytic cell 6 Working electrode;
取160ml的0.1M KOH到反应容器中,将反应容器置于磁力搅拌机上,转速设为240rpm,调整射流等离子反应器14放电端与反应容器中反应液面的距离至1cm,将等离子体电源2的电源正极12和电源负极13与射流等离子体反应器14连接,向射流等离子反应器14分别通入纯氮气、空气、N
2:O
2=9:1、N
2:O
2=7:3、N
2:O
2=6:4并通过质量流量控制计分别将总流量调整到7L/min,开启等离子体电源2,调整电压到10KV,即发生等离子液面放电反应,反应时间为10min;
Take 160ml of 0.1M KOH into the reaction vessel, place the reaction vessel on a magnetic stirrer, set the rotation speed to 240rpm, adjust the distance between the discharge end of the jet plasma reactor 14 and the reaction liquid surface in the reaction vessel to 1cm, and set the plasma power supply 2 The positive pole 12 and negative pole 13 of the power supply are connected to the jet plasma reactor 14, and the jet plasma reactor 14 is fed with pure nitrogen, air, N 2 :O 2 =9:1, N 2 :O 2 =7:3 , N 2 :O 2 =6:4 and adjust the total flow to 7L/min through the mass flow control meter, turn on the plasma power supply 2, and adjust the voltage to 10KV, that is, plasma surface discharge reaction occurs, and the reaction time is 10min;
待反应结束后,向H-型电解池6的两个反应池中分别移入50ml放电后的反应液;将所制得的工作电极、氯化银电极和铂片电极分别与电化学工作站1的工作电极夹4、参比电极夹3以及对电极夹5相连接,在CV稳定回路电流之后施加1.3V电压进行电化学催化反应,反应半小时之后将反应液吸取4ml与靛酚蓝显色剂混合,静置2小时后,根据图3所示的实验对于合成氨产率计算的标准曲线(横坐标为x表示NH
4
+浓度,纵坐标为y表示吸光度,R为该拟合曲线的线性相关度),用紫外分光光度计检测反应液中NH
4
+浓度。
After the reaction is over, transfer 50ml of the discharged reaction solution into the two reaction cells of the H-type electrolytic cell 6 respectively; combine the prepared working electrode, silver chloride electrode and platinum electrode with the electrochemical workstation 1 The working electrode clamp 4, the reference electrode clamp 3 and the counter electrode clamp 5 are connected. After the CV stabilizes the loop current, a voltage of 1.3V is applied to carry out the electrochemical catalytic reaction. After half an hour of reaction, the reaction solution is absorbed 4ml and the indophenol blue developer After mixing and standing for 2 hours, the standard curve of synthetic ammonia yield calculated according to the experiment shown in Figure 3 (the abscissa is x represents the concentration of NH 4 + , the ordinate is y represents the absorbance, and R is the linear correlation of the fitted curve ℃), use an ultraviolet spectrophotometer to detect the concentration of NH 4 + in the reaction solution.
下表为不同气体配比的反应效果对比数据:The following table shows the comparison data of the reaction effect of different gas ratios:
根据实验结果可知,当有氧气参与等离子体放电时,得到的合成氨产率较高,这是由于氧气能够提高反应后的溶液中亚硝酸根的浓度,合成氨中氮元素的来源主要为亚硝酸根。According to the experimental results, when oxygen is involved in the plasma discharge, the yield of synthetic ammonia is higher. This is because oxygen can increase the concentration of nitrite in the solution after the reaction. The source of nitrogen in synthetic ammonia is mainly nitrite. .
实施例16-19Examples 16-19
利用管式炉采用高温煅烧过渡金属催化剂的前驱物,煅烧温度范围800度,并向管式炉中通入氨气,制备不同过渡金属单原子催化剂。将制备的不同负载量0.7mg/cm
2的Cu、Fe、Ni、Co单原子催化剂、0.7μL的杜邦D520(5%wt)nafion溶液和1mL无水乙醇滴在碳纸上,烘干制得H-型电解池6的工作电极;
A tubular furnace is used to calcinate the precursor of the transition metal catalyst at a high temperature with a calcination temperature of 800 degrees, and ammonia gas is introduced into the tubular furnace to prepare different transition metal monoatomic catalysts. The prepared Cu different loading 0.7mg / cm 2 of, Fe, Ni, Co monatomic catalyst, 0.7μL DuPont D520 (5% wt) nafion solution dropwise 1mL of anhydrous ethanol in carbon paper, and drying to obtain Working electrode of H-type electrolytic cell 6;
取160ml的0.1M KOH到反应容器中,将反应容器置于磁力搅拌机上,转速设为240rpm,调整射流等离子反应器14放电端与反应容器中反应液面的距离至1cm,将等离子体电源2的电源正极12和电源负极13与射流等离子体反应器14连接,向射流等离子反应器14通入空气并通过质量流量控制计分别将流量调整到7L/min,开启等离子体电源,调整电压到10KV,即发生等离子液面放电反应,反应时间为10min;Take 160ml of 0.1M KOH into the reaction vessel, place the reaction vessel on a magnetic stirrer, set the speed to 240rpm, adjust the distance between the discharge end of the jet plasma reactor 14 and the reaction liquid surface in the reaction vessel to 1cm, and set the plasma power supply 2 The positive pole 12 of the power supply and the negative pole 13 of the power supply are connected to the jet plasma reactor 14, and air is introduced into the jet plasma reactor 14 and the flow rate is adjusted to 7L/min through the mass flow control meter. The plasma power supply is turned on and the voltage is adjusted to 10KV. , That is, plasma liquid surface discharge reaction occurs, and the reaction time is 10 minutes;
待反应结束后,向H-型电解池6的两个反应池中分别移入50ml放电后的反应液;将所制得的工作电极、氯化银电极和铂片电极分别与电化学工作站1的工作电极夹4、参比电极夹3以及对电极夹5相连接,在CV稳定回路电流之后施加1.3V电压进行电化学催化反应,反应半小时之后将反应液吸取4ml与靛酚蓝显色剂混合,静置2小时后,根据图3所示的实验对于合成氨产率计算的标准曲线(横坐标为NH
4
+浓度,纵坐标为吸光度),用紫外分光光度计检测反应液中NH
4
+浓度。
After the reaction is over, transfer 50ml of the discharged reaction solution into the two reaction cells of the H-type electrolytic cell 6 respectively; combine the prepared working electrode, silver chloride electrode and platinum electrode with the electrochemical workstation 1 The working electrode clamp 4, the reference electrode clamp 3 and the counter electrode clamp 5 are connected. After the CV stabilizes the loop current, a voltage of 1.3V is applied for electrochemical catalytic reaction. After half an hour of reaction, the reaction solution is absorbed 4ml and the indophenol blue developer After mixing and standing for 2 hours, according to the standard curve calculated for the synthetic ammonia yield in the experiment shown in Figure 3 (the abscissa is the concentration of NH 4 + , the ordinate is the absorbance), the NH 4 + in the reaction solution is detected by an ultraviolet spectrophotometer. concentration.
下表为不同过渡金属单原子催化剂的反应效果对比数据:The following table shows the comparison data of the reaction effects of different transition metal single-atom catalysts:
根据实施例结果可知,采用Co原子制备工作电极,得到的合成氨产率较高。According to the results of the examples, it can be known that using Co atoms to prepare the working electrode has a higher yield of synthetic ammonia.
实施例20-25Examples 20-25
利用管式炉采用高温煅烧过渡金属催化剂的前驱物,煅烧温度范围800度,并向管式炉 中通入氨气,制备Co单原子催化剂。将制备的不同负载量0.7mg/cm
2的Co单原子催化剂、0.7μL的杜邦D520(5%wt)nafion溶液和1mL无水乙醇滴在碳纸上,烘干制得H-型电解池6的工作电极;
A tube furnace is used to calcinate the precursor of the transition metal catalyst at a high temperature with a calcining temperature of 800 degrees, and ammonia gas is introduced into the tube furnace to prepare a Co monoatomic catalyst. The prepared Co single-atom catalysts with different loadings of 0.7 mg/cm 2 , 0.7 μL of DuPont D520 (5% wt) nafion solution and 1 mL of absolute ethanol were dropped on the carbon paper and dried to prepare an H-type electrolytic cell 6 Working electrode;
取160ml的0.1M KOH到反应容器中,将反应容器置于磁力搅拌机上,转速设为240rpm,调整射流等离子反应器14放电端与反应容器中反应液面的距离至1cm,将等离子体电源2的电源正极12和电源负极13与射流等离子体反应器14连接,向射流等离子反应器14通入空气并通过质量流量控制计分别将流量调整到7L/min,开启电源,调整电压到10KV,即发生等离子液面放电反应,反应时间为10min;Take 160ml of 0.1M KOH into the reaction vessel, place the reaction vessel on a magnetic stirrer, set the speed to 240rpm, adjust the distance between the discharge end of the jet plasma reactor 14 and the reaction liquid surface in the reaction vessel to 1cm, and set the plasma power supply 2 The positive pole 12 of the power supply and the negative pole 13 of the power supply are connected to the jet plasma reactor 14, and air is introduced into the jet plasma reactor 14 and the flow is adjusted to 7L/min through the mass flow control meter. The power is turned on and the voltage is adjusted to 10KV, namely The plasma liquid surface discharge reaction occurs, and the reaction time is 10 minutes;
待反应结束后,向H-型电解池6的两个反应池中分别移入50ml放电后的反应液;将所制得的工作电极、氯化银电极和铂片电极分别与电化学工作站1的工作电极夹4、参比电极夹3以及对电极夹5相连接,在CV稳定回路电流之后施加不同电压(1.1V-1.6V)进行电化学催化反应,反应半小时之后将反应液吸取4ml与靛酚蓝显色剂混合,静置2小时后,根据图3所示的实验对于合成氨产率计算的标准曲线(横坐标为x表示NH
4
+浓度,纵坐标为y表示吸光度,R为该拟合曲线的线性相关度),用紫外分光光度计检测反应液中NH
4
+浓度。
After the reaction is over, transfer 50ml of the discharged reaction solution into the two reaction cells of the H-type electrolytic cell 6 respectively; combine the prepared working electrode, silver chloride electrode and platinum electrode with the electrochemical workstation 1 The working electrode clamp 4, the reference electrode clamp 3 and the counter electrode clamp 5 are connected. After the CV stabilizes the loop current, different voltages (1.1V-1.6V) are applied to carry out the electrochemical catalytic reaction. After half an hour of reaction, the reaction solution is absorbed 4ml and The indophenol blue developer was mixed, and after standing for 2 hours, the standard curve for the yield of synthetic ammonia was calculated according to the experiment shown in Figure 3 (the abscissa is x represents the concentration of NH 4 + , the ordinate is y represents the absorbance, and R is the The linear correlation degree of the fitted curve), and the NH 4 + concentration in the reaction solution was detected with an ultraviolet spectrophotometer.
下表为电催化过程不同施加电位的反应效果对比数据:The following table is the comparison data of the reaction effect of different applied potentials in the electrocatalytic process:
根据实施例结果可知,合成氨的产率的总体趋势随电催化施加电位的增加而增加。According to the results of the examples, it can be seen that the overall trend of the yield of synthetic ammonia increases with the increase of the electrocatalytic applied potential.
实施例26-28Examples 26-28
利用管式炉采用高温煅烧过渡金属催化剂的前驱物,煅烧温度范围800度,并向管式炉中通入氨气,制备Co单原子催化剂。将制备的不同负载量0.57mg/cm
2、0.7mg/cm
2、0.86mg/cm
2的Co单原子催化剂、0.7μL的杜邦D520(5%wt)nafion溶液和1mL无水乙醇滴在碳纸上,烘干制得H-型电解池6的工作电极;
A tube furnace is used to calcinate the precursor of the transition metal catalyst at a high temperature with a calcining temperature of 800 degrees, and ammonia gas is introduced into the tube furnace to prepare a Co monoatomic catalyst. Different loading produced 0.57mg / cm 2, 0.7mg / cm 2, 0.86mg / cm Co monoatomic catalyst 2, 0.7μL DuPont D520 (5% wt) nafion solution and 1mL of anhydrous ethanol dropwise carbon paper On top, the working electrode of the H-shaped electrolytic cell 6 is obtained by drying;
取160ml的0.1M KOH到反应容器中,将反应容器置于磁力搅拌机上,转速设为240rpm,调整射流等离子反应器14放电端与反应容器中反应液面的距离至1cm,将等离子体电源2的 电源正极12和电源负极13与射流等离子体反应器14连接,向射流等离子反应器14通入空气并通过质量流量控制计分别将流量调整到7L/min,开启等离子体电源2,调整电压到10KV,即发生等离子液面放电反应,反应时间为10min;Take 160ml of 0.1M KOH into the reaction vessel, place the reaction vessel on a magnetic stirrer, set the speed to 240rpm, adjust the distance between the discharge end of the jet plasma reactor 14 and the reaction liquid surface in the reaction vessel to 1cm, and set the plasma power supply 2 The positive electrode 12 of the power supply and the negative electrode 13 of the power supply are connected to the jet plasma reactor 14. Air is introduced into the jet plasma reactor 14 and the flow rate is adjusted to 7L/min through the mass flow control meter. The plasma power supply 2 is turned on and the voltage is adjusted to 10KV, that is, plasma liquid surface discharge reaction occurs, and the reaction time is 10min;
待反应结束后,向H-型电解池6的两个反应池中分别移入50ml放电后的反应液;将所制得的工作电极、氯化银电极和铂片电极分别与电化学工作站1的工作电极夹4、参比电极夹3以及对电极夹5相连接,在CV稳定回路电流之后施加1.3V电压进行电化学催化反应,反应半小时之后将反应液吸取4ml与靛酚蓝显色剂混合,静置2小时后,根据图3所示的实验对于合成氨产率计算的标准曲线(横坐标为x表示NH
4
+浓度,纵坐标为y表示吸光度,R为该拟合曲线的线性相关度),用紫外分光光度计检测反应液中NH
4
+浓度。
After the reaction is over, transfer 50ml of the discharged reaction solution into the two reaction cells of the H-type electrolytic cell 6 respectively; combine the prepared working electrode, silver chloride electrode and platinum electrode with the electrochemical workstation 1 The working electrode clamp 4, the reference electrode clamp 3 and the counter electrode clamp 5 are connected. After the CV stabilizes the loop current, a voltage of 1.3V is applied for electrochemical catalytic reaction. After half an hour of reaction, the reaction solution is absorbed 4ml and the indophenol blue developer After mixing and standing for 2 hours, the standard curve of synthetic ammonia yield calculated according to the experiment shown in Figure 3 (the abscissa is x represents the concentration of NH 4 + , the ordinate is y represents the absorbance, and R is the linear correlation of the fitted curve ℃), use an ultraviolet spectrophotometer to detect the concentration of NH 4 + in the reaction solution.
下表为不同催化剂负载量的反应效果对比数据:The following table shows the comparison data of the reaction effect of different catalyst loadings:
根据实施例结果可知,当催化剂负载量为0.86mg/cm
2时,得到的合成氨产率最高。
According to the results of the examples, when the catalyst loading is 0.86 mg/cm 2 , the yield of synthetic ammonia obtained is the highest.
采用本发明的方法,所得合成氨的产率远远高于现有的常规通过电催化得到合成氨的产率。By adopting the method of the present invention, the yield of obtained synthetic ammonia is much higher than the existing conventional yield of synthetic ammonia obtained by electrocatalysis.
实施例30Example 30
利用管式炉采用高温煅烧过渡金属催化剂的前驱物,煅烧温度范围800度,并向管式炉中通入氨气,制备Co单原子催化剂。将制备的不同负载量0.7mg/cm
2的Co单原子催化剂、0.7μL的杜邦D520(5%wt)nafion溶液和1mL无水乙醇滴在碳纸上,烘干制得H-型电解池6的工作电极;
A tube furnace is used to calcinate the precursor of the transition metal catalyst at a high temperature with a calcining temperature of 800 degrees, and ammonia gas is introduced into the tube furnace to prepare a Co monoatomic catalyst. The prepared Co single-atom catalysts with different loadings of 0.7 mg/cm 2 , 0.7 μL of DuPont D520 (5% wt) nafion solution and 1 mL of absolute ethanol were dropped on the carbon paper and dried to prepare an H-type electrolytic cell 6 Working electrode;
各取50ml 0.1M KOH溶液至H型电解池的两个反应池中,将H型电解池置于磁力搅拌机上,转速设为240rpm,调整射流等离子反应器14放电端与H型电解池中反应液面的距离至1cm,将等离子体电源2的电源正极12和电源负极13与射流等离子体反应器14连接,向射流等离子反应器14通入空气并通过质量流量控制计分别将流量调整到7L/min,开启电源,调整电压到10KV,即发生等离子液面放电反应,反应时间可在5-30分钟内调节,等离子放电反应开始的同时,开启电化学工作站将所制得的工作电极、氯化银电极和铂片电极分别与电化学工作站1的工作电极夹4、参比电极夹3以及对电极夹5相连接,在CV稳定回路电流之 后施加1.3V电压进行电化学催化反应,反应半小时之后将反应液吸取4ml与靛酚蓝显色剂混合,静置2小时后用紫外分光光度计检测反应液中NH
4
+浓度。
Take 50ml of 0.1M KOH solution into the two reaction cells of the H-shaped electrolytic cell, place the H-shaped electrolytic cell on a magnetic stirrer, set the speed to 240 rpm, and adjust the discharge end of the jet plasma reactor 14 to react with the H-shaped electrolytic cell. The distance of the liquid surface is 1cm, the power supply positive electrode 12 and the power supply negative electrode 13 of the plasma power supply 2 are connected to the jet plasma reactor 14, and air is introduced into the jet plasma reactor 14 and the flow rate is adjusted to 7L through the mass flow controller. /min, turn on the power supply, adjust the voltage to 10KV, and then the plasma level discharge reaction will occur. The reaction time can be adjusted within 5-30 minutes. At the same time as the plasma discharge reaction starts, turn on the electrochemical workstation to remove the prepared working electrode and chlorine. The silver electrode and the platinum sheet electrode are respectively connected to the working electrode holder 4, the reference electrode holder 3 and the counter electrode holder 5 of the electrochemical workstation 1. After the CV stabilizes the loop current, a voltage of 1.3V is applied to carry out the electrochemical catalytic reaction. After hours, 4 ml of the reaction solution was absorbed and mixed with the indophenol blue developer, and after standing for 2 hours, the NH 4 + concentration in the reaction solution was detected by an ultraviolet spectrophotometer.
该模式为在线检测模式,相对于离线模式,该方法可以通过对液面进行长时间的处理从而源源不断地提供含氮物质,同时将H型电解池与射流等离子反应器这两个装置结合在一起,操作更加方便,控制更加灵活。This mode is an online detection mode. Compared with the offline mode, this method can continuously provide nitrogen-containing substances by treating the liquid surface for a long time. At the same time, the two devices of the H-type electrolytic cell and the jet plasma reactor are combined in Together, the operation is more convenient and the control is more flexible.
本发明方法在合成氨的同时,伴随着NO
x、硝酸等氧化固氮产物的制备。耦合低温等离子体和单原子催化剂两个处理工艺,既保证了对于氮气高效的活化,也保证了合成氨的选择性,并基于产生氧化固氮产物实现了高效的经济性。相较于目前合成氨效果实现了一个很大的提升,而且目前实验装置在不断改进,有望在之后达到更加好的效果。
The method of the present invention, while ammonia, along with the oxidation product prepared nitrogenase NO x, and nitric acid. The two treatment processes of coupling low-temperature plasma and single-atom catalyst not only ensure the high-efficiency activation of nitrogen, but also ensure the selectivity of ammonia synthesis, and realize high-efficiency economy based on the production of oxidized nitrogen fixation products. Compared with the current synthetic ammonia effect, it has achieved a great improvement, and the current experimental equipment is continuously improved, and it is expected to achieve better results in the future.
上述实施例用来解释说明本发明,而不是对本发明进行限制,在本发明的精神和权利要求的保护范围内,对本发明作出的任何修改和改变,都落入本发明的保护范围。The above-mentioned embodiments are used to explain the present invention, not to limit the present invention. Any modification and change made to the present invention within the spirit of the present invention and the protection scope of the claims shall fall into the protection scope of the present invention.
Claims (6)
- 一种低温射流等离子体耦合单原子催化的固氮装置,其特征在于,该装置包括电化学工作站(1)、等离子体电源(2)、H-型电解池(6)和射流等离子体反应器(14);A low-temperature jet plasma coupled single-atom catalysis nitrogen fixing device, characterized in that the device includes an electrochemical workstation (1), a plasma power supply (2), an H-type electrolytic cell (6) and a jet plasma reactor ( 14);所述电化学工作站(1)包括参比电极夹(3)、工作电极夹(4)和对电极夹(5)等;所述等离子体电源(2)包括电源正极(12)和电源负极(13)。The electrochemical workstation (1) includes a reference electrode clamp (3), a working electrode clamp (4), a counter electrode clamp (5), etc.; the plasma power source (2) includes a positive electrode (12) and a negative electrode ( 13).所述H-型电解池(6)包括第一氩气进口(7)、第一氩气出口(8)、质子交换膜(9)、第二氩气进口(10)和第二氩气出口(11)等;所述H-型电解池(6)的参比电极与电化学工作站(1)中的参比电极夹(3)相连接,所述H-型电解池(6)的工作电极与电化学工作站(1)中的工作电极夹(4)相连接,所述H-型电解池(6)的对电极与电化学工作站(1)中的对电极夹(5)相连接,形成电催化过程的回路。The H-type electrolytic cell (6) includes a first argon gas inlet (7), a first argon gas outlet (8), a proton exchange membrane (9), a second argon gas inlet (10) and a second argon gas outlet (11) etc.; the reference electrode of the H-type electrolytic cell (6) is connected with the reference electrode clamp (3) in the electrochemical workstation (1), and the work of the H-type electrolytic cell (6) The electrode is connected with the working electrode clamp (4) in the electrochemical workstation (1), and the counter electrode of the H-type electrolytic cell (6) is connected with the counter electrode clamp (5) in the electrochemical workstation (1), Form the circuit of the electrocatalytic process.所述射流等离子体反应器(14)包括內电极、外电极和气体通道,所述内电极与等离子体电源(2)的电源正极(12)连接,所述外电极与等离子体电源(2)的电源负极(13)连接;所述气体通道用于通入气体,使射流等离子体反应器(14)中的射流等离子体放电。The jet plasma reactor (14) includes an inner electrode, an outer electrode, and a gas channel. The inner electrode is connected to the positive electrode (12) of the plasma power source (2), and the outer electrode is connected to the plasma power source (2). The negative electrode (13) of the power supply is connected; the gas channel is used to pass in gas to discharge the jet plasma in the jet plasma reactor (14).所述质子交换膜(9)在两个H-型电解池(6)之间,防止因气体扩散而影响正负极反应的进行。The proton exchange membrane (9) is between the two H-type electrolytic cells (6) to prevent gas diffusion from affecting the progress of the positive and negative reactions.
- 一种低温射流等离子体耦合单原子催化的固氮方法,其特征在于,该固氮方法为离线运行模式,包括以下步骤:A low-temperature jet plasma coupled single-atom catalysis nitrogen fixation method is characterized in that the nitrogen fixation method is an offline operation mode and includes the following steps:(1)利用管式炉高温煅烧过渡金属催化剂的前驱物,煅烧温度为800度,并向管式炉中通入氨气,制备过渡金属单原子催化剂。所述过渡金属催化剂的前驱物包括生长在炭基底上的Cu、Fe、Ni、Co的金属粒子;(1) The precursor of the transition metal catalyst is calcined at a high temperature in a tube furnace at a calcination temperature of 800 degrees, and ammonia gas is introduced into the tube furnace to prepare the transition metal monoatomic catalyst. The precursor of the transition metal catalyst includes Cu, Fe, Ni, Co metal particles grown on a carbon substrate;(2)将步骤(1)制备的过渡金属单原子催化剂、质量分数为5%的萘酚溶液和无水乙醇混合后,刷在碳纸上,烘干制得H-型电解池(6)的工作电极,其中,萘酚溶液和无水乙醇的体积比为7:10000,过渡金属单原子催化剂的负载量为0.57mg/cm 2~0.86mg/cm 2; (2) After mixing the transition metal monoatomic catalyst prepared in step (1), the naphthol solution with a mass fraction of 5% and anhydrous ethanol, brush on carbon paper and dry to obtain an H-type electrolytic cell (6) In the working electrode, the volume ratio of naphthol solution and absolute ethanol is 7:10000, and the loading amount of transition metal monoatomic catalyst is 0.57mg/cm 2 ~0.86mg/cm 2 ;(3)将空气、氮气或者氧气和氮气混合气体直接通入射流等离子体反应器(14);并利用质量流量计调节进入射流等离子体反应器(14)的气体的流量和比例,所述氧气和氮气混合气体中氧气和氮气的体积比为4:6~1:9;调节气体流量为4L/min~8L/min;打开等离子体电源(2),利用等离子体电源(2)调节输入射流等离子体反应器(14)两端的功率,实现射流等离子体稳定的放电,调节射流等离子体反应器(14)的放电端与反应容器中的液面距离在1cm-5cm之间;射流等离子体反应器(14)放电10分钟后,关闭等离子体电源(2);(3) Directly pass air, nitrogen or a mixed gas of oxygen and nitrogen into the incident flow plasma reactor (14); and use a mass flow meter to adjust the flow rate and proportion of the gas entering the jet plasma reactor (14), the oxygen The volume ratio of oxygen and nitrogen in the mixed gas with nitrogen is 4:6~1:9; the gas flow is adjusted to 4L/min~8L/min; the plasma power supply (2) is turned on, and the plasma power supply (2) is used to adjust the input jet The power at both ends of the plasma reactor (14) realizes the stable discharge of jet plasma. Adjust the distance between the discharge end of the jet plasma reactor (14) and the liquid surface in the reaction vessel to be between 1cm-5cm; jet plasma reaction After the device (14) is discharged for 10 minutes, turn off the plasma power supply (2);(4)向H型电解池(6)的两个反应池中分别移入50ml放电之后的反应液,同时经过 第一氩气进口(7)和第二氩气进口(10)向H-型电解池(6)中的电解液中通入氩气,实现除氧;氩气从第一氩气出口(8)和第二氩气出口(11)流出;(4) Transfer 50ml of the reaction solution after discharge into the two reaction cells of the H-type electrolysis cell (6), and at the same time pass through the first argon inlet (7) and the second argon inlet (10) to the H-type electrolysis Argon gas is passed into the electrolyte in the cell (6) to achieve deoxygenation; the argon gas flows out from the first argon gas outlet (8) and the second argon gas outlet (11);(5)开启电化学工作站(1)并运行CV使得电流稳定后,在1.1V-1.6V的施加电压下进行30min电化学催化过程,收集H-型电解池(6)中的反应后的含有NH 4 +溶液。 (5) Turn on the electrochemical workstation (1) and run the CV to make the current stable, perform an electrochemical catalysis process at an applied voltage of 1.1V-1.6V for 30 minutes, and collect the reacted content in the H-type electrolytic cell (6) NH 4 + solution.
- 根据权利要求2所述的一种低温射流等离子体耦合单原子催化的固氮方法,其特征在于,该固氮方法为在线运行模式;所述在线运行模式中,射流等离子体反应器(14)固定在H-型电解池(6)中,放电端与H-型电解池(6)中的溶液直接反应;制得H-型电解池(6)的工作电极后,并调节参数与离线运行时一致,同时打开等离子体电源(2)和电化学工作站(1),并进行除氧,除氧方式与离线运行一致,等离子体电源(2)和电化学工作站(1)的工作时间以及电化学工作站(1)施加的电压均与离线运行模式保持一致,实现合成氨反应,收集H-型电解池(6)中的反应后的含有NH 4 +溶液。 The method for nitrogen fixation with low-temperature jet plasma coupled with single atom catalysis according to claim 2, wherein the nitrogen fixation method is an online operation mode; in the online operation mode, the jet plasma reactor (14) is fixed at In the H-type electrolytic cell (6), the discharge end directly reacts with the solution in the H-type electrolytic cell (6); after the working electrode of the H-type electrolytic cell (6) is prepared, the adjustment parameters are consistent with those in offline operation , Turn on the plasma power supply (2) and electrochemical workstation (1) at the same time, and perform deoxygenation. The deoxygenation method is the same as offline operation. The working time of the plasma power supply (2) and electrochemical workstation (1) and the electrochemical workstation (1) The applied voltage is consistent with the offline operation mode to realize the synthesis of ammonia reaction, and collect the reacted NH 4 + solution in the H-type electrolytic cell (6).
- 根据权利要求3所述的一种低温射流等离子体耦合单原子催化的固氮方法,其特征在于,离线运行模式中反应容器中的溶液与在线运行模式H-型电解池(6)中的溶液均为0.1MKOH溶液。The method for fixing nitrogen with low temperature jet plasma coupled single atom catalysis according to claim 3, characterized in that the solution in the reaction vessel in the offline operation mode is equal to the solution in the H-type electrolytic cell (6) in the online operation mode. It is a 0.1MKOH solution.
- 根据权利要求2所述的一种应用低温射流等离子体耦合单原子催化的固氮装置的方法,其特征在于,运行过程中,收集H-型电解池(6)的气体产物,并用气相色谱分析测试产生的气态固氮产物的浓度。The method of applying low-temperature jet plasma coupled monoatomic catalysis nitrogen fixation device according to claim 2, characterized in that, during operation, the gas products of the H-type electrolytic cell (6) are collected and analyzed and tested by gas chromatography The concentration of gaseous nitrogen fixation products produced.
- 根据权利要求2所述的一种应用低温射流等离子体耦合单原子催化的固氮装置的方法,其特征在于,取4ml在H-型电解池(6)中反应后的含有NH 4 +溶液,加入靛酚蓝显色溶液后静置两小时后得到不同颜色深度的绿色溶液;利用紫外-分光光度计测试得到的溶液,获得合成氨的产率。 The method of applying low-temperature jet plasma coupled monoatomic catalysis nitrogen fixation device according to claim 2, characterized in that 4ml of the NH 4 + solution after the reaction in the H-type electrolytic cell (6) is taken and added After the indophenol blue coloring solution was allowed to stand for two hours, green solutions with different color depths were obtained; the obtained solution was tested with an ultraviolet-spectrophotometer, and the yield of synthetic ammonia was obtained.
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