CN110963504B - Application of black phosphorus material in photoelectric nitrogen fixation - Google Patents
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- CN110963504B CN110963504B CN201911244518.9A CN201911244518A CN110963504B CN 110963504 B CN110963504 B CN 110963504B CN 201911244518 A CN201911244518 A CN 201911244518A CN 110963504 B CN110963504 B CN 110963504B
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 60
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000000463 material Substances 0.000 title claims abstract description 32
- 239000000758 substrate Substances 0.000 claims abstract description 6
- 239000011521 glass Substances 0.000 claims description 23
- 239000003792 electrolyte Substances 0.000 claims description 21
- 229910052724 xenon Inorganic materials 0.000 claims description 11
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 11
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910001873 dinitrogen Inorganic materials 0.000 claims 3
- 239000002055 nanoplate Substances 0.000 claims 2
- 239000006260 foam Substances 0.000 claims 1
- 230000001678 irradiating effect Effects 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 38
- 229910021529 ammonia Inorganic materials 0.000 abstract description 19
- 238000000034 method Methods 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 239000002086 nanomaterial Substances 0.000 abstract description 4
- 239000007864 aqueous solution Substances 0.000 abstract 2
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 abstract 1
- 238000001704 evaporation Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- 230000007935 neutral effect Effects 0.000 abstract 1
- 231100000252 nontoxic Toxicity 0.000 abstract 1
- 230000003000 nontoxic effect Effects 0.000 abstract 1
- 238000007650 screen-printing Methods 0.000 abstract 1
- 238000004528 spin coating Methods 0.000 abstract 1
- 238000005507 spraying Methods 0.000 abstract 1
- 238000002835 absorbance Methods 0.000 description 25
- 238000006243 chemical reaction Methods 0.000 description 19
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 239000002135 nanosheet Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 5
- 229910052737 gold Inorganic materials 0.000 description 5
- 239000010931 gold Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- 239000012086 standard solution Substances 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000005518 electrochemistry Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 238000002267 linear dichroism spectroscopy Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- -1 transition metal chalcogenide Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- 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
- C01C1/0411—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst characterised by the catalyst
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Hybrid Cells (AREA)
- Photovoltaic Devices (AREA)
- Catalysts (AREA)
Abstract
The invention provides a black phosphorus material photoelectric nitrogen fixation application, which is characterized in that a black phosphorus material is prepared into an electrode and used as a photoelectric catalyst to convert nitrogen into ammonia. In the method, a black phosphorus material is directly used as an electrode, or a black phosphorus material dispersion liquid is fixed on a substrate without nitrogen fixation activity by a spraying, spin coating, screen printing and heating evaporation method, and the black phosphorus material is applied to photoelectric nitrogen fixation in an acidic, neutral and alkaline aqueous solution. The black phosphorus and the black phosphorus nano material based on the black phosphorus are non-toxic and non-pollution, have excellent and stable photoelectric nitrogen fixation performance, have performance in aqueous solutions with various pH values, and are widely applicable to places.
Description
Technical Field
The invention belongs to the field of nano material application, and relates to an application of a black phosphorus material in photoelectric nitrogen fixation.
Background
Ammonia is closely related to human daily life and is the reaction substrate in the synthesis of many chemical products, such as fertilizers. On the other hand, ammonia is also an ideal hydrogen energy carrier candidate. The hydrogen energy converted from natural energy such as wind energy and solar energy is an ideal sustainable energy, and ammonia contains three hydrogen atoms and has high hydrogen content. The products of the ammonia combustion reaction are nitrogen and water, have no carbon content and are green energy sources. And the ammonia is easy to liquefy and convenient to transport. Currently, the industrial process for producing ammonia is the H-B process, which requires high temperature and pressure, and does not require carbonaceous materials for the reaction process, however, one of the participating materials is CO, and the synthesized CO produces carbonaceous contaminants. At present, the clean energy light energy and electric energy are combined to convert nitrogen into ammonia in a solution containing H protons at normal temperature and normal pressure, and the process is nitrogen reduction. The conversion process has no pollution and the device is simple. However, in the system, while the generated nitrogen is reduced, a competitive side reaction hydrogen evolution reaction occurs, and when an excessively high negative voltage is applied to the system, the side reaction is excessively strong, and the nitrogen generation reaction is suppressed, so that the ammonia yield is reduced. In addition, the activity of the existing nitrogen anti-procatalyst is low. Therefore, it is very important to find a catalyst which can inhibit the hydrogen evolution reaction and has a high activity.
Black phosphorus is a crystal with metallic luster, has a black and flaky structure, and is the most attractive one of allotropes of elemental phosphorus. Since black phosphorus has excellent semiconductor characteristics, it is one of the most potential two-dimensional semiconductors following graphene and transition metal chalcogenide. Black phosphorus has an adjustable direct bandgap and, when the number of layers and size are appropriate, has a high carrier mobility (up to 6.5X 10) 4 cm 2 V.s), very large on-off ratio characteristic (10) 4 ～10 5 ) And significant anisotropy; besides, the material also has good heat conduction performance, thermoelectric performance, photovoltaic effect, polarized light response in a field effect transistor, linear dichroism, high-frequency vibration nano electromechanical effect and the like. The black phosphorus has wide application prospect in the fields of electrochemistry, photoelectric devices, optics and the like. The black phosphorus has good nitrogen adsorption capacity, and the H-shaped semiconductor structure carrier of the black phosphorus is a hole, so that the hydrogen evolution reaction is inhibited. The black phosphorus can absorb light energy of all wave bands and has strong absorption capacity. In conclusion, black phosphorus has great potential in photoelectrocatalysis of nitrogen counter-origin. Therefore, further research is needed on how to apply black phosphorus in photoelectric nitrogen fixation to play its specific role. At present, no relevant report exists on the application of the method.
Disclosure of Invention
In view of the above problems, the present invention aims to provide a nanomaterial capable of producing ammonia under photoelectric conditions, wherein the method is simple, easy, safe and reliable, free of pollutants and capable of reacting at normal temperature and normal pressure.
The invention provides a black phosphorus nano material for converting nitrogen into ammonia by photoelectrocatalysis, and the photoelectricity nitrogen fixation process comprises the following steps:
(1) The black phosphorus material is directly used as a working electrode or fixed on a conductive substrate to be used as the working electrode, is placed in electrolyte, and is tested for the photoelectric nitrogen fixation performance conventionally.
(2) Two independent glass cups are connected into an electrolytic cell by using a Rough gold capillary, one glass cup is used as an anode and used for placing a counter electrode, the other glass cup is used as a cathode and used for placing a working electrode and a reference electrode. A300W xenon lamp is used as a light source, light is irradiated from the side face of a cathode glass cup, the side which is not irradiated is reflected by tinfoil, the reaction environment is ensured to be uniformly illuminated, electrolyte is added into an electrolytic cell twice, the mixture is magnetically stirred, 99.999 percent of nitrogen is introduced into the electrolyte, and after the electrolyte is saturated with the nitrogen, the nitrogen is continuously introduced at a certain speed.
(3) The working electrode, the reference electrode and the counter electrode are connected with the electrochemical workstation one by one, and different constant voltages are applied for a period of time.
(4) Collecting the catholyte, spectrophotometrically measuring NH therein 4 + And (4) concentration. Mixing a predetermined amount of supernatant with a predetermined amount of Neusler reagent, measuring absorbance in a spectrophotometer, and collecting NH 4 + Recording the absorbance value at the position with the maximum absorbance of 650nm, and then comparing the absorbance value with the absorbance of the ammonia nitrogen standard solution to finally obtain the concentration of ammonia nitrogen in the reaction solution, thereby converting the concentration into the photocatalytic nitrogen fixation efficiency in unit time.
In the step (1), the black phosphorus material can be block black phosphorus, black phosphorus nanosheets with different thicknesses, and a composite of the black phosphorus nanosheets and other materials.
In the step (1), the selected conductive substrate can be a titanium mesh, a titanium sheet, foamed nickel, carbon cloth, a glassy carbon sheet and conductive glass.
In the step (2), the power of the xenon lamp can be adjusted, and the power is 0.1-10 times of sunlight.
Preferably, the power of the xenon lamp is 1 to 2 times of the sunlight.
In the step (2), the electrolyte is pH 0-14, and comprises 0.1M HCl and 0.1M KOH.
In the step (2), the speed of magnetic stirring is 100-1000rup/s.
In the step (2), the speed of introducing nitrogen is 10-1000CC/s.
In the step (3), the applied voltage is 0.01V-2V.
Preferably, the applied voltage is 0.1-0.5V.
In the step (3), the voltage is applied for 0.001-10h.
Preferably, the voltage is applied for a period of 1-10 hours.
The invention has the beneficial effects that:
1. the invention adopts an electrochemical technology to provide voltage, uses a black phosphorus material as a catalyst, converts nitrogen into ammonia under the action of light, has safe and easy operation in the reaction process, does not generate pollutants, and can react at normal temperature and normal pressure;
2. in the invention, the black phosphorus material is used as a catalyst, and the photoelectric nitrogen fixation efficiency is high. The black phosphorus has good light absorption and can absorb sunlight of all wave bands. The black phosphorus is an H-type semiconductor and has weaker hydrogen evolution reaction, so that the side reaction competition is reduced, and the nitrogen fixation performance is enhanced. The black phosphorus has a plurality of nitrogen fixation active sites and is a potential photoelectric nitrogen fixation catalyst.
Drawings
FIG. 1 is a white light chart of a black phosphor crystal according to example 1;
FIG. 2 is a graph showing the yield of ammonia produced in example 3.
Detailed Description
Example 1
The application of the black phosphorus material in photoelectric nitrogen fixation comprises the following steps:
(1) The blocky black phosphorus crystal is directly used as a working electrode (cathode), a platinum sheet is used as a counter electrode, and saturated calomel is used as a reference electrode.
(2) Two independent glass cups are connected into an electrolytic cell by a Rough gold capillary, one glass cup is used as an anode and is used as a counter electrode, and the other glass cup is used as a cathode and is used as a working electrode and a reference electrode. A300W xenon lamp is used as a light source, the power is 1 sunlight, the side surface of a cathode glass cup is irradiated with light, the side which is not irradiated is reflected by tinfoil, the reaction environment is ensured to be uniformly illuminated, the electrolyte is added into the electrolytic cell for two times, a magnetic stirrer is used for stirring at 100rup/s, 99.999 percent of nitrogen is introduced into the electrolyte, and after the electrolyte is saturated with the nitrogen, the nitrogen is continuously introduced at the speed of 10 CC/s.
(3) The working electrode, the reference electrode and the counter electrode are connected with the electrochemical workstation one by one, and 0.1-0.5V voltage of a section of 0.5h is applied.
(4) Collecting the catholyte, and measuring by spectrophotometryIn the amount of NH 4 + And (4) concentration. Mixing a predetermined amount of supernatant with a predetermined amount of Nesler reagent, measuring absorbance in a spectrophotometer, and collecting NH 4 + Recording the absorbance value at the position with the maximum absorbance of 650nm, and then comparing the absorbance value with the absorbance of the ammonia nitrogen standard solution to finally obtain the concentration of ammonia nitrogen in the reaction solution, thereby converting the concentration into the photocatalytic nitrogen fixation efficiency in unit time. The ammonia yield is 1ug/h/cm 2 。
Example 2
The application of the black phosphorus material in photoelectric nitrogen fixation comprises the following steps:
(1) The black phosphorus nanosheet prepared by ultrasonic is dripped on conductive glass to serve as a working electrode (cathode), the area of the dripping is 1 square centimeter, and the content of the dripping is 1mg. The nanosheet is 5 nanometers thick and has a lateral dimension of 200 nanometers. The platinum sheet is used as a counter electrode, and the saturated calomel is used as a reference electrode.
(2) Two independent glass cups are connected into an electrolytic cell by a Rough gold capillary, one glass cup is used as an anode and is used as a counter electrode, and the other glass cup is used as a cathode and is used as a working electrode and a reference electrode. A300W xenon lamp is used as a light source, the power is 1 sunlight, the side of a cathode glass cup is irradiated with light, the side which is not irradiated is reflected by tinfoil, the reaction environment is ensured to be uniformly illuminated, electrolyte is added into an electrolytic cell twice, a magnetic stirrer is used for stirring at 1000rup/s, 99.999 percent of nitrogen is introduced into the electrolyte, and after the electrolyte is saturated with the nitrogen, the nitrogen is continuously introduced at the speed of 1000CC/s.
(3) The working electrode, the reference electrode and the counter electrode are connected with the electrochemical workstation one by one, and 0.1-0.5V voltage of a section of 10h is applied.
(4) Collecting the catholyte, spectrophotometrically measuring the NH content 4 + And (4) concentration. Mixing a predetermined amount of supernatant with a predetermined amount of Nesler reagent, measuring absorbance in a spectrophotometer, and collecting NH 4 + Recording the absorbance value at the position with the maximum absorbance of 650nm, and then comparing the absorbance value with the absorbance of the ammonia nitrogen standard solution to finally obtain the concentration of ammonia nitrogen in the reaction solution, thereby converting the concentration into the photocatalytic nitrogen fixation efficiency in unit time. The ammonia yield is 28ug/h/cm 2 。
Example 3
The application of the black phosphorus material in photoelectric nitrogen fixation comprises the following steps:
(1) The electrochemically prepared black phosphorus nanosheet (with the lateral dimension of 1 micron and the thickness of 5 nanometers) and cobalt particles (with the diameter of 200 nanometers) are ultrasonically mixed together, and the mixture is dripped on a glassy carbon sheet to be used as a working electrode (cathode), the area of the dripping is 1 square centimeter, and the content of the dripping is 0.5mg. The platinum sheet is a counter electrode, the saturated calomel is a reference electrode, and the electrolyte is 0.1m hydrochloric acid.
(2) Two independent glass cups are connected into an electrolytic cell by using a Rough gold capillary, one glass cup is used as an anode and used for placing a counter electrode, the other glass cup is used as a cathode and used for placing a working electrode and a reference electrode. A300W xenon lamp is used as a light source, the power is 2 sunlight, the side of a cathode glass cup is irradiated with light, the side which is not irradiated is reflected by tinfoil, the reaction environment is ensured to be uniformly illuminated, electrolyte is added into an electrolytic cell twice, a magnetic stirrer is used for stirring at 600rup/s, 99.999 percent of nitrogen is introduced into the electrolyte, and after the electrolyte is saturated with the nitrogen, the nitrogen is continuously introduced at the speed of 100 CC/s.
(3) The working electrode, the reference electrode and the counter electrode are connected with the electrochemical workstation one by one, and 0.1-0.5V voltage of a section of 2h is applied.
(4) Collecting the catholyte, spectrophotometrically measuring NH therein 4 + And (4) concentration. Mixing a predetermined amount of supernatant with a predetermined amount of Nesler reagent, measuring absorbance in a spectrophotometer, and collecting NH 4 + Recording the absorbance value at the position with the maximum absorbance of 650nm, and then comparing the absorbance value with the absorbance of the ammonia nitrogen standard solution to finally obtain the concentration of ammonia nitrogen in the reaction solution, thereby converting the concentration into the photocatalytic nitrogen fixation efficiency in unit time. When the voltage is increased from 0.3V to 0.4V, the ammonia yield is gradually increased, when the voltage is continuously applied, the side reaction is intensified, the side reaction occupies a catalytic active site, the ammonia yield is gradually reduced, and the maximum ammonia yield is 26.3ug/h/cm 2 。
Example 4
The application of the black phosphorus material in photoelectric nitrogen fixation comprises the following steps:
(1) The black phosphorus nanosheet (with the lateral dimension of 1 micron and the thickness of 5 nanometers) prepared by electrochemistry and molybdenum disulfide (with the diameter of 200 nanometers) are ultrasonically and uniformly mixed, and the black phosphorus molybdenum sulfide compound is dripped on carbon paper to be used as a working electrode (cathode), wherein the area of the dripping is 1 square centimeter, and the content is 0.5mg. The platinum sheet is a counter electrode, the saturated calomel is a reference electrode, and the electrolyte is 0.1m sodium sulfate.
(2) Two independent glass cups are connected into an electrolytic cell by a Rough gold capillary, one glass cup is used as an anode and is used as a counter electrode, and the other glass cup is used as a cathode and is used as a working electrode and a reference electrode. A300W xenon lamp is used as a light source, the power of the xenon lamp is 1.5 sunlight, the xenon lamp illuminates from the side surface of a cathode glass cup, the side which is not illuminated reflects by tinfoil, the reaction environment is ensured to be uniformly illuminated, electrolyte is added into an electrolytic cell for two times, a magnetic stirrer is used for stirring at 600rup/s, 99.999 percent of nitrogen is introduced into the electrolyte, and after the electrolyte is saturated with the nitrogen, the nitrogen is continuously introduced at the speed of 100 CC/s.
(3) The working electrode, the reference electrode and the counter electrode are connected with the electrochemical workstation one by one, and 0.1-0.5V voltage of a section of 2h is applied.
(4) Collecting the catholyte, spectrophotometrically measuring NH therein 4 + And (4) concentration. Mixing a predetermined amount of supernatant with a predetermined amount of Neusler reagent, measuring absorbance in a spectrophotometer, and collecting NH 4 + Recording the absorbance value at the position of 650nm with the maximum absorbance, and then comparing the absorbance value with the absorbance of the ammonia nitrogen standard solution to finally obtain the concentration of the ammonia nitrogen in the reaction solution, thereby converting the concentration into the photocatalytic nitrogen fixation efficiency in unit time. The ammonia yield is 8ug/h/cm 2 。
Claims (8)
1. The application of the black phosphorus material in photoelectric nitrogen fixation is characterized by comprising the following steps:
(1) Directly using a black phosphorus material as a working electrode or fixing the black phosphorus material on a conductive substrate as the working electrode, and placing the black phosphorus material in electrolyte;
(2) Introducing nitrogen into the electrolytic cell, continuously stirring, and irradiating the working electrode with light;
(3) The working electrode and the reference electrode are connected with the counter electrode and the electrochemical workstation one by one, and voltage is applied for a period of time;
(4) Collecting the catholyte and testing for NH 4 + And (4) calculating the nitrogen fixation efficiency.
2. The use of the black phosphorus material in photoelectric nitrogen fixation according to claim 1, wherein the black phosphorus material in step (1) includes, but is not limited to, bulk black phosphorus, black phosphorus nanoplates of different thicknesses, and composites of black phosphorus nanoplates with other materials.
3. The use of the black phosphorus material in photoelectric nitrogen fixation according to claim 1, wherein the conductive substrate in step (1) includes but is not limited to titanium mesh, titanium sheet, nickel foam, carbon cloth, glassy carbon sheet, conductive glass.
4. The application of the black phosphorus material in photoelectric nitrogen fixation according to claim 1, wherein the light in the step (2) is irradiated by a xenon lamp, the power of the xenon lamp is adjustable, and the power is 0.1-10 times of sunlight.
5. The use of the black phosphorus material in photoelectric nitrogen fixation according to claim 1, wherein the stirring rate in the step (2) is 100-1000rup/s.
6. The application of the black phosphorus material in photoelectric nitrogen fixation according to claim 1, wherein the nitrogen gas is introduced in the step (2) at a rate of 10-1000CC/s, and after the electrolyte is saturated with the nitrogen gas, the nitrogen gas is continuously introduced at a certain rate.
7. The use of the black phosphorus material in photoelectric nitrogen fixation according to claim 1, wherein the voltage applied in the step (3) is 0.01V-2V.
8. The use of the black phosphorus material in photoelectric nitrogen fixation according to claim 1, wherein the voltage is applied in the step (3) for 0.001-10h.
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| WO2009147126A1 (en) * | 2008-06-03 | 2009-12-10 | Basf Se | Titanium dioxide composition comprising titanium dioxide nanoparticles, and preparation and use thereof |
| CN106335885A (en) * | 2016-08-17 | 2017-01-18 | 深圳先进技术研究院 | Black phosphorus nanosheet and preparation method and application thereof |
| CN109420512A (en) * | 2017-09-04 | 2019-03-05 | 中国科学院上海硅酸盐研究所 | A kind of catalysis material and its preparation method and application based on phosphoric acid modification |
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