CN115074756A - Bimetal-doped porous carbon nanofiber catalyst and preparation method and application thereof - Google Patents
Bimetal-doped porous carbon nanofiber catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a bimetal doped porous carbon nanofiber catalyst and a preparation method and application thereof, wherein the method comprises the following steps: sequentially mixing polyacrylonitrile, N-N dimethylformamide, ZnO, cobalt nitrate hexahydrate and lithium carbonate, and fully stirring to obtain a spinning precursor solution; performing electrostatic spinning on the spinning precursor solution to obtain a cobalt nitrate/lithium carbonate/ZnO/polyacrylonitrile nanofiber membrane; carrying out pre-oxidation treatment on the nanofiber membrane in an air atmosphere to obtain a pre-oxidized nanofiber membrane; and placing the pre-oxidized nanofiber membrane in an inert atmosphere for carbonization treatment, and cooling to room temperature to obtain the bimetal-doped porous carbon nanofiber catalyst. The preparation method is simple, the raw material cost is low, the reaction condition is mild, the large-scale production is facilitated, the catalyst has excellent performance for electrochemically reducing nitrate, the generation rate of ammonia is higher than that of an industrial method, and the catalyst has guiding significance for the industrial use of electrochemically reducing nitrate.
Description
Technical Field
The invention relates to the field of preparation of electrochemical bimetal-doped porous carbon nanofiber catalysts, in particular to a bimetal-doped porous carbon nanofiber catalyst and a preparation method and application thereof.
Background
Ammonia (NH) 3 ) Is the most basic chemical raw material, which is not only an indispensable chemical for preparing fertilizers, medicines, dyes and the like, but also is considered as an important energy storage medium and a carbon-free energy carrier. Currently, NH is synthesized industrially 3 Still using the Haber-Bosch process, the process needs to be carried out under harsh operating conditions, i.e., at high temperatures (400-. Synthesis of NH due to its large annual yield and energy consumption process 3 Industry accounts for 1-2% of the total energy consumption of the world, and discharged carbon dioxide (CO) 2 ) The amount is about 2% of the total greenhouse gases. In recent years, nitrogen (N) has been electrocatalyzed 2 ) Reduction Reactions (NRR) are of interest in the ammonia synthesis industry, but are limited in their industrial applications due to their high energy consumption, low reaction rates, selectivity and faradaic efficiency. Electrochemical reduction of Nitrate (NO) 3 - ) Is NH 3 Compared with the Haber-Bosch process and the NRR, the method is more energy-saving, has wide sources of nitrate in nature, and has great significance for solving the two problems of energy and environment by converting the nitrate into ammonia through electrocatalysis.
In recent years, because of high preparation cost of noble metal catalysts, reports of replacing noble metal catalysts with non-noble metals are increasing day by day, but because of generally low current density of non-noble metal catalysts and poor ammonia selectivity, competitive hydrogen evolution reaction exists, and raw materials of some non-noble metal catalysts have high cost and complex preparation process, and large-scale production is difficult to realize and apply to industry.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a bimetallic-doped porous carbon nanofiber catalyst, and a preparation method and application thereof, and aims to solve the problems that the non-noble metal catalyst in the existing electrochemical reduction nitrate catalyst is low in current density, poor in ammonia selectivity, competitive in hydrogen evolution reaction and incapable of being prepared on a large scale.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of a bimetal doped porous carbon nanofiber catalyst comprises the following steps:
sequentially mixing polyacrylonitrile, N-N dimethylformamide, ZnO, cobalt nitrate hexahydrate and lithium carbonate, and fully stirring to obtain a spinning precursor solution;
performing electrostatic spinning on the spinning precursor solution to obtain a cobalt nitrate/lithium carbonate/ZnO/polyacrylonitrile nanofiber membrane;
carrying out pre-oxidation treatment on the cobalt nitrate/lithium carbonate/ZnO/polyacrylonitrile nano-fiber film in an air atmosphere to obtain a pre-oxidized nano-fiber film;
and placing the pre-oxidized nanofiber membrane in an inert atmosphere for carbonization treatment, and cooling to room temperature to obtain the bimetal-doped porous carbon nanofiber catalyst.
The preparation method of the bimetal doped porous carbon nanofiber catalyst comprises the following steps: dissolving zinc acetate dihydrate in deionized water to obtain a zinc acetate solution, dissolving triethanolamine in deionized water to obtain a triethanolamine solution, dropwise adding the zinc acetate solution into the triethanolamine solution, fully stirring, and performing ultrasonic treatment, standing, centrifugation, washing and drying to obtain ZnO.
The preparation method of the bimetal doped porous carbon nanofiber catalyst comprises the step of preparing ZnO, wherein the stirring speed is 400-600rpm, the stirring time is 5-10min, the temperature is 20-50 ℃, the ultrasonic time is 10-50min, the standing time is 10-20h, the centrifugation speed is 8000-10000rpm, the drying temperature is 50-70 ℃, the activation temperature is 400-600 ℃, and the time is 1-3 h.
The preparation method of the bimetal-doped porous carbon nanofiber catalyst comprises the following steps of mixing polyacrylonitrile, N-N dimethylformamide, ZnO, cobalt nitrate hexahydrate and lithium carbonate in sequence:
mixing N-N dimethylformamide, polyacrylonitrile, ZnO, cobalt nitrate hexahydrate and lithium carbonate in a weight ratio of 95: 8: 8: 0.3: the mixing was carried out in the order of 0.3 mass ratio.
The preparation method of the bimetal-doped porous carbon nanofiber catalyst comprises the step of fully stirring to obtain a spinning precursor solution, wherein the stirring speed is 400-600rpm, the stirring time is 12-15h, and the temperature is 20-60 ℃.
The preparation method of the bimetal doped porous carbon nanofiber catalyst comprises the following steps of: the method is characterized in that a metal needle with the inner diameter of 0.5-1.5mm is used as a nozzle, the vertical distance from the nozzle to a receiver is 10-30cm, the spinning voltage is 15-25KV, the feeding rate is 0.5-1mL/h, the spinning temperature is 30-50 ℃, and the relative air humidity is 10-90 RH%.
The preparation method of the bimetal doped porous carbon nanofiber catalyst comprises the following steps of: heating to 200 ℃ and 250 ℃ at the speed of 1-5 ℃/min, and then preserving the heat for 1-2 h.
The preparation method of the bimetal doped porous carbon nanofiber catalyst comprises the following steps of: heating to 700-.
A bi-metal doped porous carbon nanofiber catalyst prepared by the method for preparing a bi-metal doped porous carbon nanofiber catalyst according to any one of the above aspects, comprising: the nano-porous carbon nano-fiber film comprises a porous carbon nano-fiber film and cobalt-lithium nanoclusters loaded on the carbon nano-fiber film.
Use of a bimetallic doped porous carbon nanofiber catalyst as described in the above scheme for electrochemical nitrate reduction.
Has the advantages that: the invention discloses a bimetal doped porous carbon nanofiber catalyst and a preparation method and application thereof, wherein the method comprises the following steps: sequentially mixing polyacrylonitrile, N-N dimethylformamide, ZnO, cobalt nitrate hexahydrate and lithium carbonate, and fully stirring to obtain a spinning precursor solution; performing electrostatic spinning on the spinning precursor solution to obtain a cobalt nitrate/lithium carbonate/ZnO/polyacrylonitrile nanofiber membrane; carrying out pre-oxidation treatment on the cobalt nitrate/lithium carbonate/ZnO/polyacrylonitrile nanofiber membrane in an air atmosphere to obtain a pre-oxidized nanofiber membrane; and placing the pre-oxidized nanofiber membrane in an inert atmosphere for carbonization treatment, and cooling to room temperature to obtain the bimetal-doped porous carbon nanofiber catalyst. The preparation method disclosed by the invention is simple, low in raw material cost, mild in reaction conditions and convenient for large-scale production. Cobalt ions in the catalyst have an electron-deficient structure, and lithium ions adsorbed on the surface of the catalyst can effectively inhibit competitive hydrogen evolution reaction and improve the selectivity of the catalyst, and in addition, the porous structure on the surface of the catalyst increases the active surface area of the catalyst. The catalyst shows excellent performance for electrochemically reducing nitrate by virtue of the synergistic effect of cobalt and lithium ions and larger specific surface area, and the Faraday efficiency of ammonia can reach 66.1 percent at the highest under the potential of-0.82V Vs RHE, and reaches 431.9mmol g cat -1 h -1 The rate of formation of ammonia of (a) is about 2.1 times the conversion of ammonia of the Haber-Bosch reaction. The generation rate of ammonia is higher than that of an industrial method, and the method has guiding significance for the industrial use of electrochemical reduction of nitrate.
Drawings
Fig. 1 is a flowchart of a preferred embodiment of a method for preparing a bimetal-doped porous carbon nanofiber catalyst provided by the invention.
Fig. 2 is a TEM image of the bi-metal doped porous carbon nanofiber catalyst of example 1 in the present invention.
Fig. 3 is a TEM image of a bi-metal doped porous carbon nanofiber catalyst of example 3 in the present invention.
FIG. 4 is an XRD pattern of the bimetallic doped porous carbon nanofiber catalysts of examples 1-3 of the present invention.
Fig. 5 is an XPS chart of the bi-metal doped porous carbon nanofiber catalysts of examples 1-2 of the present invention.
FIG. 6 shows the addition of 0.5M KNO to the bimetal-doped porous carbon nanofiber catalyst of examples 1-2 of the present invention 3 0.5M Na of 2 SO 4 And (3) producing ammonia by a process drawing efficiency chart when electrolyzing for 1h at different potentials.
FIG. 7 shows the bimetallic doped porous carbon nanofiber catalyst of example 1 in the presence of 0.5M KNO 3 0.5M Na of 2 SO 4 And 0.5M Na 2 SO 4 Linear Sweep Voltammetry (LSV) plot of (a).
FIG. 8 shows the bimetallic doped porous carbon nanofiber catalyst of example 2 in the presence of 0.5M KNO 3 0.5M Na of 2 SO 4 And 0.5M Na 2 SO 4 Linear Sweep Voltammetry (LSV) plot of (a).
FIG. 9 shows the bimetallic doped porous carbon nanofiber catalyst of example 3 in the presence of 0.5M KNO 3 0.5M Na of 2 SO 4 And 0.5M Na 2 SO 4 Linear Sweep Voltammetry (LSV) plot of (a).
Detailed Description
The invention provides a bimetal-doped porous carbon nanofiber catalyst and a preparation method and application thereof, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and more clear. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a preparation method of a bimetal-doped porous carbon nanofiber catalyst, which comprises the following steps:
preparing a spinning precursor solution;
the spinning precursor solution is used for electrostatic spinning to prepare a nanofiber membrane;
pre-oxidizing the prepared nanofiber membrane;
and carrying out high-temperature carbonization treatment on the pre-oxidized nanofiber membrane.
Specifically, referring to fig. 1, fig. 1 is a flow chart of a preferred embodiment of a method for preparing a bimetal-doped porous carbon nanofiber catalyst according to the present invention, as shown in fig. 1, which includes the steps of:
s100, preparing a spinning precursor solution: sequentially mixing polyacrylonitrile, N-N dimethylformamide, ZnO, cobalt nitrate hexahydrate and lithium carbonate, and fully stirring to obtain a spinning precursor solution;
s200, electrostatic spinning: performing electrostatic spinning on the spinning precursor solution to obtain a cobalt nitrate/lithium carbonate/ZnO/polyacrylonitrile nanofiber membrane;
s300, pre-oxidation treatment: carrying out pre-oxidation treatment on the cobalt nitrate/lithium carbonate/ZnO/polyacrylonitrile nano-fiber film in an air atmosphere to obtain a pre-oxidized nano-fiber film;
s400, high-temperature carbonization treatment: and placing the pre-oxidized nanofiber membrane in an inert atmosphere for carbonization treatment, and cooling to room temperature to obtain the bimetal-doped porous carbon nanofiber catalyst.
The method comprises the steps of dissolving polyacrylonitrile, ZnO, cobalt nitrate hexahydrate and lithium carbonate in N-N Dimethylformamide (DMF) solvent in sequence to prepare spinning precursor solution, and then obtaining the bimetal doped porous carbon nanofiber catalyst by electrostatic spinning, pre-oxidation treatment and high-temperature carbonization treatment by adopting an electrostatic spinning technology, wherein the bimetal doped porous carbon nanofiber catalyst prepared by the method has certain mechanical strength and can be used for electrochemical nitrate radical reduction, and the method has the following advantages:
(1) the preparation method of the bimetal-doped porous carbon nanofiber catalyst is simple, the raw material cost is low, the reaction condition is mild, and large-scale production can be realized;
(2) the cobalt-doped nanoclusters of the bimetallic-doped porous carbon nanofiber catalyst can be used as active sites for electrocatalysis of nitrate radical reduction;
(3) the lithium-doped nanoclusters of the bimetallic-doped porous carbon nanofiber catalyst have a good adsorption effect on nitrate radicals enriched on the surface of the catalyst, and are catalytically reduced into ammonia;
(4) the prepared bimetal doped porous carbon nanofiber catalyst has excellent mechanical properties;
(5) the surface of the bimetal-doped porous carbon nanofiber catalyst contains rich porous structures and has a large specific surface area;
(6) the prepared bimetal doped porous carbon nanofiber catalyst has wide application prospect in the field of electrochemical nitrate radical reduction catalysts.
The mechanism of the present invention is explained in detail below: the nano fiber membrane prepared by electrostatic spinning is subjected to pre-oxidation treatment, so that the concentration of the nano fiber membrane can be increased, the rigidity of fibers is properly enhanced, and the nano fiber structure is not easy to break and is more stable through carbonization treatment.
In this embodiment, the preparation method of ZnO includes the steps of: dissolving zinc acetate dihydrate in deionized water to obtain a zinc acetate solution, dissolving triethanolamine in deionized water to obtain a triethanolamine solution, dropwise adding the zinc acetate solution into the triethanolamine solution, fully stirring, and performing ultrasonic treatment, standing, centrifugation, washing and drying to obtain ZnO.
In some preferred embodiments, the ZnO needs to be activated in a muffle furnace before the spinning precursor solution is prepared.
In some embodiments, in the step of preparing ZnO, the stirring rate is 400-600rpm, the stirring time is 5-10min, the temperature is 20-50 ℃, the ultrasonic time is 10-50min, the standing time is 10-20h, the centrifugation rate is 8000-10000rpm, the drying temperature is 50-70 ℃, the activation temperature is 400-600 ℃ and the time is 1-3 h.
In this embodiment, the step of sequentially mixing polyacrylonitrile, N-N dimethylformamide, ZnO, cobalt nitrate hexahydrate, and lithium carbonate specifically includes:
mixing N-N dimethylformamide, polyacrylonitrile, ZnO, cobalt nitrate hexahydrate and lithium carbonate in a weight ratio of 95: 8: 8: 0.3: the mixing was carried out in sequence at a mass ratio of 0.3, at which it was advantageous to form fibers of uniform diameter during electrospinning.
Specifically, adding N-N dimethylformamide into polyacrylonitrile, and magnetically stirring to obtain a viscous transparent solution; adding ZnO, and magnetically stirring to obtain viscous milky white solution; continuously adding cobalt nitrate hexahydrate, and magnetically stirring to obtain a viscous purple solution; and continuously adding lithium carbonate, and magnetically stirring to obtain a spinning precursor solution.
In some embodiments, in the step of sufficiently stirring to obtain the spinning precursor solution, the stirring speed is 400-600rpm, the stirring time is 12-15h, the temperature is 20-60 ℃, and a uniformly dispersed spinning precursor solution is easily obtained under the conditions.
In this embodiment, the electrostatic spinning process parameters are as follows: the method is characterized in that a metal needle with the inner diameter of 0.5-1.5mm is used as a nozzle, the vertical distance from the nozzle to a receiver is 10-30cm, the spinning voltage is 15-25KV, the feeding rate is 0.5-1mL/h, the spinning temperature is 30-50 ℃, the relative air humidity is 10-90 RH%, and the diameter of the obtained fiber can be uniformly distributed by selecting the parameters.
In some embodiments, the step of pre-oxidation treatment specifically comprises: the temperature is raised to 250 ℃ at the speed of 1-5 ℃/min, and then the temperature is kept for 1-2h, the rigidity of the nanofiber membrane can be enhanced through pre-oxidation treatment, so that the nanofiber membrane is not easy to break in the high-temperature calcination process.
In some embodiments, the step of carbonizing specifically comprises: raising the temperature to 700-1000 ℃ at the speed of 1-10 ℃/min, and then preserving the temperature for 1-3h, wherein the inert atmosphere of the carbonization treatment is preferably high-purity argon or nitrogen with the purity of more than or equal to 99.99 percent.
The invention also provides a bimetal doped porous carbon nanofiber catalyst prepared by the preparation method of the bimetal doped porous carbon nanofiber catalyst in any one of the schemes, which comprises the following steps: the nano-porous carbon nano-fiber film comprises a porous carbon nano-fiber film and cobalt-lithium nanoclusters loaded on the carbon nano-fiber film.
The bimetallic doped porous carbon nanofiber catalyst prepared by the invention mainly provides electrochemical activity by two factors: the synergy and porous structure of cobalt lithium nanoclusters. Wherein, the cobalt ions have an electron-deficient structure, can provide active sites and increase the current density; the lithium ions can effectively inhibit the hydrogen evolution reaction, and nitrate radicals are enriched on the surface of the catalyst, so that the selectivity of the product is improved; the porous structure is helpful for increasing the specific surface area of the reaction and improving the reactivity.
The invention also provides application of the bimetal doped porous carbon nanofiber catalyst in electrochemical nitrate reduction.
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The nitrogen used in the embodiment is high-purity nitrogen with the purity of more than or equal to 99.99 percent; other chemicals used, unless otherwise specified, were obtained from conventional commercial sources.
Example 1
Adding 10mLN-N dimethylformamide into 0.8g polyacrylonitrile, and magnetically stirring for 5h to obtain a viscous transparent solution; then adding 0.8g of ZnO, and magnetically stirring for 12 hours to obtain a viscous milky white solution; continuously adding 0.03g of cobalt nitrate hexahydrate, and magnetically stirring for 5 hours to obtain a viscous purple solution; and then, continuously adding 0.03g of lithium carbonate, and magnetically stirring for 12 hours to obtain a spinning precursor solution. Performing electrostatic spinning on the obtained spinning precursor solution, and collecting a cobalt acid/lithium carbonate/ZnO/polyacrylonitrile nanofiber membrane; the electrostatic spinning parameters are as follows: a metal needle with the inner diameter of 0.8mm is used as a spray head, the spinning voltage is 21KV, the vertical distance from the needle to a receiver is 15cm, the feeding speed is 0.7mL/h, the spinning temperature is 30 ℃, the air relative humidity is 20 RH%, and the round drum aluminum foil receives spinning fibers. Placing the cobalt nitrate hexahydrate/lithium carbonate/ZnO/polyacrylonitrile nanofiber membrane obtained in the last step in a muffle furnace, heating to 220 ℃ at the speed of 1 ℃/min in the air atmosphere, preserving heat for 1h, and carrying out pre-oxidation treatment to obtain a pre-oxidized nanofiber membrane; and (3) placing the pre-oxidized nanofiber membrane obtained in the previous step into a tubular furnace, heating to 900 ℃ at the speed of 5 ℃/min under the protection of nitrogen atmosphere, preserving heat for 2h, carrying out carbonization treatment, and cooling to room temperature to obtain the carbonized bimetal-doped porous carbon nanofiber catalyst.
Nitrate was electrochemically reduced using the catalyst material produced in example 1 to produce ammonia.
Ethanol was first mixed with 2 wt.% Nafion 117 membrane solution in a volume ratio of 980: 20 to prepare Nafion diluent, adding 1mg of bimetal doped porous carbon nanofiber catalyst into 100 mu of the Nafion diluent for uniform ultrasonic dispersion, then uniformly dripping the dispersion on 0.5cm by 0.5cm carbon paper washed by 1mol/L hydrochloric acid, ethanol and deionized water by using a 10 mu of a pipetting gun, and drying a working electrode by using an infrared lamp to obtain the Nafion composite membrane. An Ag/AgCl electrode is used as a reference electrode, and a Pt electrode is used as an auxiliary electrode; the cathode chamber of the H tank is provided with a working electrode and a reference electrode, argon is introduced to remove oxygen, the anode chamber is provided with an auxiliary electrode, and the two electrode chambers are separated by an anion exchange membrane FAB-PK-130. Respectively at 0.5MKNO 3 0.5M Na of 2 SO 4 Aqueous solution and 0.5M Na 2 SO 4 The aqueous solution is used as electrolyte, and the test is carried out at room temperature and normal pressure.
Example 2
Adding 10mLN-N dimethylformamide into 0.8g polyacrylonitrile, and magnetically stirring for 5h to obtain a viscous transparent solution; then adding 0.8g of ZnO, and magnetically stirring for 12 hours to obtain a viscous milky white solution; and continuously adding 0.03g of cobalt nitrate hexahydrate, and magnetically stirring for 12 hours to obtain a spinning precursor solution. Performing electrostatic spinning on the obtained spinning precursor solution, and collecting a cobalt nitrate hexahydrate/ZnO/polyacrylonitrile nanofiber membrane; the electrostatic spinning parameters are as follows: a metal needle with the inner diameter of 0.8mm is used as a spray nozzle, the spinning voltage is 21KV, the vertical distance from the needle to a receiver is 15cm, the feeding speed is 0.7mL/h, the spinning temperature is 30 ℃, the relative air humidity is 20 RH%, and a round roller aluminum foil receives spinning fibers. Placing the cobalt hexahydrate/lithium carbonate/ZnO/polyacrylonitrile nanofiber membrane obtained in the last step into a muffle furnace, heating to 220 ℃ at the speed of 1 ℃/min in the air atmosphere, preserving heat for 1h, and carrying out pre-oxidation treatment to obtain a pre-oxidized nanofiber membrane; and (3) placing the pre-oxidized nanofiber membrane obtained in the previous step into a tubular furnace, heating to 900 ℃ at the speed of 5 ℃/min under the protection of nitrogen atmosphere, preserving heat for 2 hours, carrying out carbonization treatment, and cooling to room temperature to obtain the carbonized cobalt metal doped porous carbon nanofiber catalyst.
Nitrate was electrochemically reduced using the catalyst material produced in example 2 to produce ammonia.
Ethanol was first mixed with 2 wt.% Nafion 117 membrane solution in a volume ratio of 980: 20 to prepare Nafion diluent, adding 1mg of cobalt metal doped porous carbon nanofiber catalyst into 100 mu of Nafion diluent for uniform ultrasonic dispersion, then uniformly dripping the dispersion on 0.5cm by 0.5cm carbon paper washed by 1mol/L hydrochloric acid, ethanol and deionized water by using a 10 mu of pipette gun, and drying the working electrode by using an infrared lamp to obtain the catalyst. An Ag/AgCl electrode is used as a reference electrode, and a Pt electrode is used as an auxiliary electrode; the cathode chamber of the H tank is provided with a working electrode and a reference electrode, argon is introduced to remove oxygen, the anode chamber is provided with an auxiliary electrode, and the two electrode chambers are separated by an anion exchange membrane FAB-PK-130. Respectively at 0.5MKNO 3 0.5M Na of 2 SO 4 Aqueous solution and 0.5M Na 2 SO 4 The aqueous solution is an electrolyte and is tested under the conditions of room temperature and normal pressure.
Example 3
Adding 10mLN-N dimethylformamide into 0.8g polyacrylonitrile, and magnetically stirring for 5h to obtain a viscous transparent solution; then 0.03g of cobalt nitrate hexahydrate is added, and the mixture is magnetically stirred for 12 hours to obtain a spinning precursor solution. Performing electrostatic spinning on the obtained spinning precursor solution, and collecting a cobalt nitrate hexahydrate/polyacrylonitrile nanofiber membrane; the electrostatic spinning parameters are as follows: a metal needle with the inner diameter of 0.8mm is used as a spray head, the spinning voltage is 21KV, the vertical distance from the needle to a receiver is 15cm, the feeding speed is 0.7mL/h, the spinning temperature is 30 ℃, the air relative humidity is 20 RH%, and the round drum aluminum foil receives spinning fibers. Placing the cobalt nitrate hexahydrate/polyacrylonitrile nanofiber membrane obtained in the last step into a muffle furnace, heating to 220 ℃ at the speed of 1 ℃/min in the air atmosphere, preserving heat for 1h, and performing pre-oxidation treatment to obtain a pre-oxidized nanofiber membrane; and (3) placing the pre-oxidized nano fiber membrane obtained in the last step into a tubular furnace, heating to 900 ℃ at the speed of 5 ℃/min under the protection of nitrogen atmosphere, preserving heat for 2h, carrying out carbonization treatment, and cooling to room temperature to obtain the carbonized cobalt metal doped carbon nano fiber catalyst.
Nitrate was electrochemically reduced using the catalyst material produced in example 3 to produce ammonia.
Ethanol was first mixed with 2 wt.% Nafion 117 membrane solution in a volume ratio of 980: 20 to prepare Nafion diluent, adding 1mg of cobalt metal doped carbon nanofiber catalyst into 100 mu of Nafion diluent for uniform ultrasonic dispersion, then uniformly dripping the dispersion on 0.5cm by 0.5cm carbon paper washed by 1mol/L hydrochloric acid, ethanol and deionized water by using a 10 mu of pipette gun, and drying the working electrode by using an infrared lamp to obtain the catalyst. An Ag/AgCl electrode is used as a reference electrode, and a Pt electrode is used as an auxiliary electrode; the cathode chamber of the H tank is provided with a working electrode and a reference electrode, argon is introduced to remove oxygen, the anode chamber is provided with an auxiliary electrode, and the two electrode chambers are separated by an anion exchange membrane FAB-PK-130. Respectively at 0.5MKNO 3 0.5M Na of 2 SO 4 Aqueous solution and 0.5M Na 2 SO 4 The aqueous solution is an electrolyte and is tested under the conditions of room temperature and normal pressure.
The test results of the above examples are shown in fig. 2-9.
FIG. 2 is a TEM image of the bimetal doped porous carbon nanofiber catalyst of example 1 in the present invention, as shown in FIG. 2, the surface of the catalyst of example 1 is distributed with many pores, and the diameter of the pores is about 150 nm; similar to the diameter of ZnO.
Fig. 3 is a TEM image of the bi-metal doped porous carbon nanofiber catalyst of example 3 of the present invention, as shown in fig. 3, the catalyst of example 3 has a smooth surface without significant pores.
Fig. 4 is an XRD chart of the bimetal doped porous carbon nanofiber catalysts of examples 1 to 3 in the present invention, as shown in fig. 4, the catalysts of examples 1 to 3 have two peaks at 24.1 and 44.1 °, respectively corresponding to (002) and (100) crystal planes of carbon, and have no other obvious peak. The above characterization preliminarily proves that the cobalt and lithium elements loaded in the examples 1-3 exist in the form of nanoclusters.
FIG. 5 is an XPS plot of the bimetallic doped porous carbon nanofiber catalysts of examples 1-2 of the present invention, as shown in FIG. 5, the catalyst of example 1 has a peak at 55.05eV, while the catalyst of example 2 has no peak, indicating that no lithium ion is present in example 2.
FIG. 6 is a graph showing the faradaic efficiency of ammonia generated by electrolyzing the bimetal-doped porous carbon nanofiber catalyst of examples 1-2 in 0.5M Na2SO4 of 0.5M KNO3 for 1h, as shown in FIG. 6, in 2 catalysts, the faradaic efficiency of ammonia generated by the catalyst of example 1 is kept above 55% at most in the potential interval of 0.79-0.89V Vs RHE, and the maximum faradaic efficiency of ammonia is 66.1% at the potential of-0.82V Vs RHE, SO that the ammonia generation rate of 431.9mmol g cat-1h-1 is better than that of the catalyst of example 2. The lithium ion is proved to be capable of promoting the nitrate radical enrichment capacity on the surface of the catalyst and converting the nitrate radical into ammonia, thereby improving the product selectivity of the catalyst.
FIG. 7 shows the bimetallic doped porous carbon nanofiber catalyst of example 1 at 0.5M KNO 3 0.5M Na of 2 SO 4 And 0.5M Na 2 SO 4 LSV in aqueous solution, electrochemical testing was performed in an electrochemical testing system (CHI 760E, CH Instrument Inc) with a H cell as the testing apparatus, carbon paper loaded with a catalyst as the working electrode, a platinum electrode as the auxiliary electrode, and Ag/AgCl as the reference electrode, as shown in FIG. 7, and the current density in example 1 was 404.6mA/cm 2 Hydrogen evolution reactionThe current density is 179.8mA/cm 2 . The current density of the embodiment 1 is better than that of the embodiments 2-3, and the hydrogen evolution reaction can be obviously inhibited. The lithium ion added into the catalyst is proved to promote the synergistic effect of cobalt and lithium and improve the current density.
FIG. 8 shows the bimetallic doped porous carbon nanofiber catalyst of example 2 at 0.5M KNO 3 0.5M Na of 2 SO 4 And 0.5M Na 2 SO 4 LSV in aqueous solution, electrochemical test was performed in an electrochemical test system (CHI 760E, CH Instrument Inc) with a H cell as a test apparatus, carbon paper loaded with a catalyst as a working electrode, a platinum electrode as an auxiliary electrode, and Ag/AgCl as a reference electrode, as shown in FIG. 8, and the current density in example 2 was 304.5mA/cm 2 The current density of the hydrogen evolution reaction is 251.3mA/cm 2 . The current density of this example 2 is intermediate to examples 1 and 3, indicating that the addition of ZnO to increase the surface area of the catalyst helps to increase the active surface area of the catalyst, increasing the current density.
FIG. 9 shows the bimetallic doped porous carbon nanofiber catalyst of example 3 in 0.5M KNO 3 0.5M Na of 2 SO 4 And 0.5M Na 2 SO 4 LSV in aqueous solution, electrochemical testing was performed in an electrochemical testing system (CHI 760E, CH Instrument Inc) with a H cell as the testing apparatus, carbon paper loaded with a catalyst as the working electrode, a platinum electrode as the auxiliary electrode, and Ag/AgCl as the reference electrode, as shown in FIG. 9, and the current density in example 3 was 270.5mA/cm 2 The current density of the hydrogen evolution reaction is 196.1mA/cm 2 。
In summary, the invention discloses a bimetal doped porous carbon nanofiber catalyst and a preparation method and application thereof, wherein the method comprises the following steps: sequentially mixing polyacrylonitrile, N-N dimethylformamide, ZnO, cobalt nitrate hexahydrate and lithium carbonate, and fully stirring to obtain a spinning precursor solution; performing electrostatic spinning on the spinning precursor solution to obtain a cobalt nitrate/lithium carbonate/ZnO/polyacrylonitrile nanofiber membrane; carrying out pre-oxidation treatment on the cobalt nitrate/lithium carbonate/ZnO/polyacrylonitrile nano-fiber film in an air atmosphere to obtain a pre-oxidized cobalt/lithium carbonate/ZnO/polyacrylonitrile nano-fiber filmOxidizing the nanofiber membrane; and placing the pre-oxidized nanofiber membrane in an inert atmosphere for carbonization treatment, and cooling to room temperature to obtain the bimetal-doped porous carbon nanofiber catalyst. The preparation method disclosed by the invention is simple, low in raw material cost, mild in reaction conditions and convenient for large-scale production. Cobalt ions in the catalyst have an electron-deficient structure, and lithium ions adsorbed on the surface of the catalyst can effectively inhibit competitive hydrogen evolution reaction and improve the selectivity of the catalyst, and in addition, the porous structure on the surface of the catalyst increases the active surface area of the catalyst. The catalyst shows excellent performance for electrochemically reducing nitrate by virtue of the synergistic effect of cobalt and lithium ions and larger specific surface area, and the Faraday efficiency of ammonia can reach 66.1 percent at the highest under the potential of-0.82V Vs RHE, and reaches 431.9mmol g cat -1 h -1 The generation rate of the ammonia is about 2.1 times of the conversion rate of the ammonia of the Haber-Bosch reaction, the generation rate of the ammonia is higher than that of an industrial method, and the method has guiding significance for the industrial use of electrochemical reduction of nitrate.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it should be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A preparation method of a bimetal doped porous carbon nanofiber catalyst comprises the following steps:
sequentially mixing polyacrylonitrile, N-N dimethylformamide, ZnO, cobalt nitrate hexahydrate and lithium carbonate, and fully stirring to obtain a spinning precursor solution;
performing electrostatic spinning on the spinning precursor solution to obtain a cobalt nitrate/lithium carbonate/ZnO/polyacrylonitrile nanofiber membrane;
carrying out pre-oxidation treatment on the cobalt nitrate/lithium carbonate/ZnO/polyacrylonitrile nano-fiber film in an air atmosphere to obtain a pre-oxidized nano-fiber film;
and placing the pre-oxidized nanofiber membrane in an inert atmosphere for carbonization treatment, and cooling to room temperature to obtain the bimetal-doped porous carbon nanofiber catalyst.
2. The method for preparing a bimetallic-doped porous carbon nanofiber catalyst as recited in claim 1, wherein the ZnO preparation method comprises the steps of: dissolving zinc acetate dihydrate in deionized water to obtain a zinc acetate solution, dissolving triethanolamine in deionized water to obtain a triethanolamine solution, dropwise adding the zinc acetate solution into the triethanolamine solution, fully stirring, and performing ultrasonic treatment, standing, centrifugation, washing and drying to obtain ZnO.
3. The preparation method of the bimetal doped porous carbon nanofiber catalyst as claimed in claim 2, wherein in the preparation step of ZnO, the stirring speed is 400-600rpm, the stirring time is 5-10min, the temperature is 20-50 ℃, the ultrasonic time is 10-50min, the standing time is 10-20h, the centrifugation speed is 8000-10000rpm, the drying temperature is 50-70 ℃, the activation temperature is 400-600 ℃ and the time is 1-3 h.
4. The preparation method of the bimetal-doped porous carbon nanofiber catalyst according to claim 1, wherein the step of sequentially mixing polyacrylonitrile, N-N dimethylformamide, ZnO, cobalt nitrate hexahydrate and lithium carbonate specifically comprises the following steps:
mixing N-N dimethylformamide, polyacrylonitrile, ZnO, cobalt nitrate hexahydrate and lithium carbonate in a weight ratio of 95: 8: 8: 0.3: 0.3 mass ratio was mixed in order.
5. The preparation method of the bimetal doped porous carbon nanofiber catalyst as claimed in claim 1, wherein in the step of fully stirring to obtain the spinning precursor solution, the stirring speed is 400-600rpm, the stirring time is 12-15h, and the temperature is 20-60 ℃.
6. The preparation method of the bimetal-doped porous carbon nanofiber catalyst according to claim 1, wherein the electrostatic spinning process parameters are as follows: the method is characterized in that a metal needle with the inner diameter of 0.5-1.5mm is used as a nozzle, the vertical distance from the nozzle to a receiver is 10-30cm, the spinning voltage is 15-25KV, the feeding rate is 0.5-1mL/h, the spinning temperature is 30-50 ℃, and the relative air humidity is 10-90 RH%.
7. The method for preparing a bimetallic-doped porous carbon nanofiber catalyst as claimed in claim 1, wherein the step of pre-oxidation treatment specifically comprises: heating to 200-250 ℃ at the speed of 1-5 ℃/min, and then preserving heat for 1-2 h.
8. The method for preparing a bimetallic-doped porous carbon nanofiber catalyst according to claim 1, characterized in that the carbonization treatment specifically comprises: heating to 700-.
9. A bimetallic-doped porous carbon nanofiber catalyst prepared by the method of preparing a bimetallic-doped porous carbon nanofiber catalyst as claimed in any one of claims 1 to 8, comprising: the nano-porous carbon nano-fiber film comprises a porous carbon nano-fiber film and cobalt-lithium nanoclusters loaded on the carbon nano-fiber film.
10. Use of a bi-metal doped porous carbon nanofiber catalyst as claimed in claim 9 for electrochemical nitrate reduction.
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