CN114749115A - Gas-phase photocatalytic nitrogen fixation reaction method - Google Patents
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- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/04—Preparation of ammonia by synthesis in the gas phase
- C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
- C01C1/0417—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst characterised by the synthesis reactor, e.g. arrangement of catalyst beds and heat exchangers in the reactor
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- C01C1/04—Preparation of ammonia by synthesis in the gas phase
- C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
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Abstract
The invention discloses a method for gas-phase photocatalytic nitrogen fixation reaction, which takes nitrogen and water as reactants to carry out photocatalytic nitrogen fixation under the gas-phase condition. Wherein the whole reactor is filled with reactant nitrogen, trace water pumped into the reactor is dispersed in the reactor in the form of water vapor, the catalyst is made into a catalyst plate in a dropping sheet mode and is introduced into the reactor, the reactant and the catalyst are in gas-solid contact, and the reactor is closed in the reaction process. The invention can avoid the problems of little adsorption quantity of reactant nitrogen on the catalyst caused by that the active sites of the catalyst are covered by a large amount of water, reactant waste and ammonia carrying-out of reaction products caused by that the nitrogen bubbles all the time. Compared with the existing photocatalysis nitrogen fixation reaction method, the reactant is easier to be adsorbed on the active site of the catalyst, the mass transfer is promoted, and the photocatalysis nitrogen fixation activity is improved.
Description
Technical Field
The invention belongs to the technical field of photocatalytic nitrogen fixation reaction, and particularly relates to a gas-phase photocatalytic nitrogen fixation reaction method.
Background
The photocatalytic nitrogen fixation is a nitrogen reduction reaction carried out on the surface of a catalyst under an environmental condition. Since the first application of photocatalysis to nitrogen fixation in 1977, photocatalytic nitrogen fixation has received attention from numerous scholars and has performed a great deal of work on a laboratory scale.
The photocatalysis nitrogen fixation reaction means that under the action of illumination and a catalyst, nitrogen and water undergo an oxidation-reduction reaction to generate ammonia and oxygen. The photocatalytic nitrogen fixation reaction system generally comprises a photocatalyst and reactants. The reactants are nitrogen and water.
Typical semiconductor photocatalysts are metal oxides such as titanium dioxide (TiO)2) Iron oxide (Fe)2O3) Tungsten oxide (WO)3-X) Zinc oxide (ZnO), etc.; bismuth oxyhalides such as bismuth oxybromide (BiOBr), bismuth oxychloride (BiOCl), bismuth oxyiodide (BiOI), and the like; carbon-based materials, e.g. carbon nitride (g-C)3N4) Etc.; biomimetic materials such as Fe-based proteins, MoFe proteins, and the like; metal sulfides, cadmium sulfide (CdS), molybdenum disulfide (MoS)2) And the like.
The photocatalytic nitrogen fixation reaction can be divided into two basic reactions (1) nitrogen reduction reaction protonation; (2) the oxidation reaction of water releases oxygen.
1/2 N2 + 3/2 H2O = NH3 + 3/4 O2
The photocatalytic nitrogen fixation reaction is divided into four steps, (1) adsorption of nitrogen molecules on the surface of a catalyst; (2) when the catalyst absorbs photons with a width larger than the forbidden band width of the catalyst, the photoproduction electrons are transited from the valence band to the conduction band, and holes are generated on the valence band. (3) Electrons in the conduction band undergo a reduction reaction and holes in the valence band undergo an oxidation reaction. (4) And (4) desorbing the product on the surface of the catalyst.
At present, the photocatalysis nitrogen fixation reaction is always carried out in a liquid phase, and nitrogen is continuously introduced into a catalyst-water suspension solution in a bubbling mode. The catalyst for the photocatalysis nitrogen fixation reaction is completely surrounded by water, and the nitrogen is extremely insoluble in water, so that the active sites on the catalyst are difficult to contact with the nitrogen, and even if a magnetic stirrer is used for stirring the catalyst-water suspension liquid all the time, the adsorption of the active sites to the nitrogen is greatly weakened. In addition, ammonia is very volatile, and nitrogen bubbling easily carries the generated ammonia out of the reactor.
Disclosure of Invention
The invention aims to overcome the defects of the existing liquid-phase photocatalytic nitrogen fixation reaction, provides a gas-phase photocatalytic nitrogen fixation reaction method, and aims to solve the problems of poor contact between nitrogen and a catalyst, reactor waste and reaction product carry-over caused by continuous bubbling in the liquid-phase reaction process in the existing method.
In order to realize the purpose of the invention, the invention is realized by the following technical scheme:
a simple gas-phase photocatalysis nitrogen fixation reaction method more favorable for mass transfer comprises the following steps:
step one, preparing a uniform catalyst plate which is not easy to agglomerate:
(1) uniformly dispersing the photocatalyst-water suspension on a thin glass dish;
(2) sealing the glass dish by using a preservative film;
(3) pricking holes on the preservative film by using toothpicks;
(4) the glass dish was placed in an oven and heated until the water evaporated and a film formed.
Step two, introducing a catalyst and reactants:
(1) introducing a catalyst plate (a glass dish with a film) into the reactor, covering a cover of the reactor, wherein the middle part of the cover is provided with a transparent quartz window;
（2）N2flowing the raw material gas through the reactor through an air inlet valve and an air outlet valve to remove air in the reactor, and then closing the air inlet valve and the air outlet valve;
(3) injecting trace water serving as a reactant through a sampling port of the reactor by using a trace sample injection needle; because of the trace amount of water, a water mist was formed in the reactor filled with nitrogen gas.
And step three, vertically placing a light source right above the reactor for illumination.
And step four, after illumination, injecting a small amount of ultrapure water through a sampling port of the reactor, standing for 15 minutes to dissolve the generated ammonia, and filtering the suspension liquid by using a filter port membrane to remove the catalyst for analyzing the content of the ammonia.
Further, the photocatalyst-water suspension as described in the step one (1) has a concentration of 10 mg. multidot.mL-1。
Furthermore, the thin glass vessel described in the step one (1) has an area of 5 cm2。
Further, the temperature of the oven described in the first step (4) was 60 ℃.
Moreover, the reactor in step two (1) is a conventional liquid phase reactor having a quartz window and equipped with an intake valve and an exhaust valve, a condensed water inlet/outlet, and a sampling port sealed with a silicone rubber diaphragm.
The volume of the reactor in the second step (1) was 135 mL.
And, N in the second step (2)2The flow rate of the raw material gas flowing through the reactor was 80 mL/min-1。
And, N in the second step (2)2The time for flowing through the reactor as feed gas was 40 min.
In the second step (3), the volume of the micro-amount ultrapure water injected after sealing the reactor is 10 to 40. mu.L.
And the distance between the light source and the reactor in the third step is 5 cm.
And in the fourth step, the volume of a small amount of ultrapure water is 10-50 mL after the illumination.
And, the pore diameter of the filter membrane used for filtering the catalyst in the fourth step is 0.22. mu.m.
The photocatalyst of the present invention includes powdery photocatalysts such as metal oxides, metal sulfides, carbon-based materials, bismuth-based materials, and perovskites.
The invention has the advantages and positive effects that:
the reactants are present in the reactor in the gas phase, i.e. the reaction is carried out in a gas phase reaction. The catalyst in the method of the invention is in gas-solid contact with nitrogen and water, which solves the problem of poor contact between nitrogen and the catalyst in the existing liquid phase photocatalysis nitrogen fixation reaction, and improves the activity of the photocatalysis nitrogen fixation reaction by improving the adsorption of reactants. Meanwhile, in the gas-phase photocatalytic nitrogen fixation reaction, the whole reactor is in a closed state, so that the problems of reactant waste and bringing out of a photocatalytic product ammonia caused by bubbling of nitrogen all the time in the liquid-phase reaction are solved.
Drawings
FIG. 1 is a conventional liquid phase reactor;
FIG. 2 is a schematic diagram of a catalyst plate preparation process.
Detailed Description
The gas phase photocatalysis nitrogen fixation reaction process of the invention is as follows: the catalyst plate is prepared by a dropping method, the prepared catalyst plate is introduced into a reactor, high-purity nitrogen flows through the reactor through two exhaust valves, trace ultrapure water is injected into the reactor from a sampling port, and the reaction is carried out under the illumination condition. After the reaction, a small amount of ultrapure water was poured into the reactor and left to stand to dissolve the ammonia produced. And filtering the obtained catalyst suspension by using a filter opening membrane for further ammonia nitrogen detection. The following description is of specific embodiments of the present invention in order that the present invention may be better understood by those skilled in the art.
Step one, the concentration is 10 mg/mL-1Is uniformly dispersed in an area of 5 cm2The glass dish is sealed by a preservative film and a plurality of holes are poked by toothpicks. The glass dish was then transferred to an oven at 60 ℃ and heated until the water evaporated and a film formed to produce a uniform catalyst plate that did not easily agglomerate.
Step two, the catalyst plate was introduced into a reactor having a volume of 135 mL, with a quartz window and equipped with an inlet valve and an outlet valve, a condensed water inlet and outlet, and a sampling port sealed with a silicon rubber septum, and the reactor was capped. N is a radical of280 mL/min as a raw material gas-1Flow ofThe reactor was passed for 40 min to remove air from the reactor. The gas inlet valve and the gas outlet valve are closed to seal the reactor, and 10-40 mu L of ultrapure water is injected into the reactor through a sampling port by a micro-sampling needle.
And 3, vertically placing a light source at a position 5 cm above the reactor for illumination.
Step 4, after the light irradiation, 10 to 50 mL of ultrapure water was injected into the reactor and left standing for 15 minutes to dissolve the generated ammonia. The suspension was analyzed for ammonia content by filtering off the catalyst with a filter membrane having a pore size of 0.22 μm.
Example 1
By adjusting the concentration to 10 mg. multidot.mL-1The aqueous suspension of the photocatalyst (CdS @ BiOBr) -was uniformly dispersed over an area of 5 cm2The glass dish is sealed by a preservative film and a plurality of holes are poked by toothpicks. Then transferring the glass dish to an oven at 60 ℃ for heating until water is evaporated and a film is formed to prepare a uniform catalyst plate (the amount of the catalyst is 30 mg) which is not easy to agglomerate;
the catalyst plate was introduced into a 135 mL volume reactor having a quartz window and equipped with inlet and outlet valves, a condensate inlet and outlet, and a sampling port sealed with a silicone rubber septum, and the reactor was capped. N is a radical of280 mL/min as a raw material gas-1Was flowed through the reactor for 40 min to remove air from the reactor, after which the reactor was closed. Injecting 40 mu L of ultrapure water into the reactor through a sampling port by using a micro-sampling needle, irradiating for 1 h under full-wave band to perform photocatalytic nitrogen fixation reaction, injecting 20 mL of water into the reactor after irradiation, and standing for 15 min to dissolve the generated ammonia. Filtering 5 mL of suspension with 0.22 μm filter membrane, detecting ammonia concentration by Naese reagent method, and generating amount of 2215 μ g per hour cat -1。
Meanwhile, liquid phase reaction is carried out by 30 mgCdS @ BiOBr, the catalyst is dispersed in water and is subjected to ultrasonic treatment for 10 min, and then nitrogen bubbling is carried out for 30 min under the dark condition, namely dark adsorption is carried out. Similarly, the photocatalysis nitrogen fixation reaction is carried out under the illumination of the full wave band for 1 h, 5 mL suspension is filtered by a filter opening membrane with the thickness of 0.22 mu m, the ammonia concentration is detected by a Nashin reagent method, and the generation amount of ammonia in one hour is 1559 mug·g cat -1The activity is lower than the above gas phase reaction.
The preparation method of CdS @ Bi0Br comprises the following steps: (1) 0.45 g of kBr was dissolved in 40 mL of ethylene glycol. Subsequently, 1.82 g of Bi (NO) was added3)3·5H20 was added slowly and stirred until completely dissolved. The solution was poured into a 50 mL stainless steel autoclave lined with polytetraethylene oxide, heated at 160 ℃ for 12 h, cooled and the resulting precipitate collected, washed with ethanol and ultrapure water. Drying in an oven at 60 ℃ to obtain BiOBr. (2) 0.25 g of thiourea and 0.25 g of CdCl2·2.5H20 was added to 45 mL of ultrapure water and stirred until dissolved. 0.40 g of the prepared BiOBr was dispersed in the above solvent and stirred for 3 h and transferred to a 100 mL stainless steel autoclave lined with polytetraethylene oxide. Heating at 120 deg.C for 24 h, cooling and collecting the resulting precipitate, washing with ethanol and ultrapure water. Drying in air at 60 deg.C to obtain CdS @ BiOBr.
Example 2
By adjusting the concentration to 10 mg/mL-1Uniformly dispersed in a 5 cm area2The glass dish is sealed by a preservative film and a plurality of holes are poked by toothpicks. Then transferring the glass dish to an oven at 60 ℃ for heating until water is evaporated and a film is formed to prepare a uniform catalyst plate (the catalyst amount is 50 mg) which is not easy to agglomerate;
the catalyst plate was introduced into a 135 mL volume reactor having a quartz window and equipped with inlet and outlet valves, a condensate inlet and outlet, and a sampling port sealed with a silicone rubber septum, and the reactor was capped. N is a radical of280 mL/min as a raw material gas-1Was flowed through the reactor for 40 min to remove air from the reactor, after which the reactor was closed. Injecting 40 mu L of ultrapure water into the reactor through a sampling port by using a micro-sampling needle, irradiating for 1 h under visible light to perform photocatalytic nitrogen fixation reaction, injecting 10 mL of water into the reactor after irradiation, and standing for 15 min to dissolve the generated ammonia. Filtering 5 mL suspension with 0.22 μm filter membrane, detecting ammonia concentration by Naeser reagent method, and generating ammonia amount of 383 μ g per hour cat -1。
At the same time use50mg of BiOBr is subjected to liquid phase reaction, the catalyst is dispersed in water and subjected to ultrasonic treatment for 10 min, and then nitrogen bubbling is carried out for 30 min under the dark condition, namely dark adsorption is carried out. Similarly, the photocatalytic nitrogen fixation reaction was performed by irradiation with visible light for 1 hour, 5 mL of the suspension was filtered through a 0.22 μm filter, and the ammonia concentration was measured by the Naeseler reagent method, whereby the amount of ammonia produced per hour was 254. mu.g.g cat -1The activity is lower than that of the above gas phase reaction.
Preparation of BiOBr:
0.45 g of kBr was dissolved in 40 mL of ethylene glycol. Subsequently, 1.82 g of Bi (NO)3)3·5H20 was added slowly and stirred until completely dissolved. The solution was poured into a 50 mL stainless steel autoclave lined with polytetraethylene oxide, heated at 160 ℃ for 12 h, cooled and the resulting precipitate collected, washed with ethanol and ultrapure water. Drying in an oven at 60 ℃ to obtain BiOBr.
The above-described embodiments are only preferred embodiments of the present invention, and other types of embodiments may be implemented, and those skilled in the art may make corresponding changes according to the present invention, but these changes should fall within the scope of the present invention.
Claims (10)
1. A method for gas-phase photocatalysis nitrogen fixation reaction is characterized by comprising the following steps:
step one, preparing a uniform catalyst film which is not easy to agglomerate: uniformly dispersing the photocatalyst-water suspension on a plane carrier, and then heating until water is evaporated and a catalyst film is formed;
step two, introducing a catalyst and reactants:
(1) introducing the catalyst plate into the reactor, and covering the cover of the reactor;
(2) with N2Introducing raw material gas into the reactor to remove air in the reactor, then closing the gas inlet and the gas outlet, injecting trace water through a sampling port of the reactor, vertically placing a light source right above the reactor for illumination, and performing photocatalytic nitrogen fixation reaction;
and step three, after the reaction is finished, injecting water through a sampling port of the reactor and standing to dissolve the generated ammonia.
2. The method for gas-phase photocatalytic nitrogen fixation reaction of claim 1, wherein the concentration of the photocatalyst-water suspension in the first step is 10 mg/mL.
3. The method of claim 1, wherein the flat carrier in the first step is a thin glass plate.
4. The method for gas-phase photocatalytic nitrogen fixation reaction according to claim 1, wherein the heating temperature in the first step is 60 ℃.
5. The method of claim 1, wherein the reactor in step two is a conventional liquid phase reactor having a quartz window and equipped with an inlet and an outlet valve, a condensed water inlet and outlet, and a sampling port.
6. The method for gas-phase photocatalytic nitrogen fixation reaction of claim 1, wherein N in step two2The flow rate through the reactor as the raw material gas was 80 mL/min.
7. The gas-phase photocatalytic nitrogen fixation reaction method as claimed in claim 1, wherein N in the second step2The time for flowing through the reactor as feed gas was 40 min.
8. The method for gas-phase photocatalytic nitrogen fixation reaction as recited in claim 1, wherein in the second step, the volume of the injected micro-amount of ultrapure water after sealing the reactor is 10-40 μ L.
9. The method for gas-phase photocatalytic nitrogen fixation reaction according to claim 1, wherein the distance from the light source to the reactor in the second step is 5 cm.
10. The method for gas-phase photocatalytic nitrogen fixation reaction of claim 1, wherein the volume of a small amount of ultrapure water added into the reactor after the light irradiation in the third step is 10-50 mL.
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| CN116081640A (en) * | 2022-12-20 | 2023-05-09 | 清华大学 | Synthesis method and device of green ammonia |
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| CN107855130A (en) * | 2017-11-23 | 2018-03-30 | 大连工业大学 | A kind of solar energy fixed nitrogen photochemical catalyst and application thereof and preparation method |
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