CN111933961B - Binary CoFe alloy loaded g-C3N4Catalyst and preparation method thereof - Google Patents
Binary CoFe alloy loaded g-C3N4Catalyst and preparation method thereof Download PDFInfo
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
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- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
Abstract
The invention provides a binary CoFe alloy loaded g-C3N4The catalyst and the preparation method thereof comprise the following steps: synthesis of sheet-like two-dimensional porous g-C3N4And dispersed in deionized water; respectively dispersing zinc salt, cobalt salt and iron salt in deionized water; dispersing 2-methylimidazole and polyvinylpyrrolidone in deionized water; mixing the solutions obtained in the steps S1, S2 and S3, performing water bath reaction, stirring at room temperature, centrifuging, and drying in vacuum to obtain CoFe @ g-C3N4(ii) a The resulting CoFe @ g-C3N4Calcining in a tubular furnace to obtain g-C3N4Supported Co/CoFe-NC @ g-C3N4A material. The technical scheme of the invention is adopted to obtain Co/CoFe-NC @ g-C3N4Materials, commercial Pt/C and RuO2Compared with the prior art, the catalyst has good catalytic activity, stability and durability; the preparation process is simple and controllable.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a binary CoFe alloy loaded g-C3N4A catalyst and a preparation method thereof.
Background
Increasingly severe energy crisis put high demands on environmentally friendly, safe, reliable, high energy density new energy conversion systems. Currently promising energy systems include metal air cells (MAB), fuel cells, and metal ion batteries. Among them, zinc-air batteries are attracting attention as one of the fuel cells because of their higher theoretical energy density and higher earth reserves. The key to zinc air cell (ZAB) technology is the study of highly efficient and stable electrocatalysts for the cathode Oxygen Reduction Reaction (ORR) and the anode Oxygen Evolution Reaction (OER).
Commercial catalysts currently used on ZAB in ORR and OER are based on noble metals, Pt/C and IrO respectively2/RuO2Catalysts, however, have limited large-scale use due to cost and stability issues. Therefore, the development of the low-cost and high-activity bifunctional electrocatalyst has important significance for the technical development of future fuel cells.
Various non-noble metal-based catalysts containing carbon supports have been developed for ORR and OER. The results show that the catalyst based on carbon doped with non-metal elements (N, S, O, P and the like) or transition metals (Co, Fe, Ni, Zn and the like) has better catalytic activity due to the heteroatom doping and modified electronic structure. Of all the catalysts, cobalt-based catalysts have attracted considerable attention. Co, present as metallic Co, Co-M alloys and Co-Nx on carbonaceous supports, were all identified as having active sites for ORR and OER. In fact, they can effectively modulate the electronic structure of the carbon-containing support and reduce the adsorption energy of the intermediates, thereby reducing the overpotentials of ORR and OER. In addition, the electronic synergistic effect between metal elements can further improve the electrocatalytic performance based on binary or ternary component catalysts. However, the synthesis of CoFe catalysts is currently performed through a high energy-consuming route, and it is difficult to simultaneously achieve miniaturization of metal particles and also to suppress migration and aggregation thereof.
Disclosure of Invention
Aiming at the technical problems, the invention discloses a binary CoFe alloy loaded g-C3N4The catalyst and the preparation method thereof have the high-efficiency dual-function functions of oxygen reduction and oxygen precipitation, and can avoid the agglomeration of nano metal particles.
In contrast, the technical scheme adopted by the invention is as follows:
binary CoFe alloy loaded g-C3N4The preparation method of the catalyst comprises the following steps:
step S1, synthesizing sheet-shaped two-dimensional porous g-C3N4And dispersed in deionized water;
step S2, respectively dispersing zinc salt, cobalt salt and iron salt in deionized water;
step S3, dispersing 2-methylimidazole and polyvinylpyrrolidone in deionized water;
step S4, willMixing the solutions obtained in the steps S1, S2 and S3, performing water bath reaction, stirring at room temperature, centrifuging, and performing vacuum drying to obtain CoFe @ g-C3N4；
Step S5, obtaining CoFe @ g-C3N4Calcining in a tubular furnace to obtain g-C3N4Supported Co/CoFe-NC @ g-C3N4A material.
By adopting the technical scheme, the zinc metal zeolite imidazole compound and Co are subjected to one-pot reaction2+And Fe3+And g-C3N4The g-C is prepared by combining hydrothermal synthesis and sintering processes of a tube furnace3N4Highly dispersed, high catalytic activity Co nanoparticles and CoFe alloys on nanosheets, the catalysts being useful in zinc-air cell reactions with ORR and OER occurring at the cathode, with commercial Pt/C and RuO2In contrast, the binary CoFe alloy supports g-C3N4The catalyst has good catalytic activity, stability and durability.
As a further improvement of the invention, in step S1, the sheet-like two-dimensional porous g-C3N4The preparation method comprises the following steps: placing melamine in a crucible, heating at 550 deg.C for 2 h in a muffle furnace, and heating at 500 deg.C for 2 h to obtain sheet-like porous g-C3N4A material.
As a further improvement of the invention, in step S2, the molar ratio of the zinc salt to the cobalt salt is 1: 0.8-1.2. Further, the molar ratio of the zinc salt to the cobalt salt is 1: 1.
as a further improvement of the present invention, in step S2, the zinc salt is zinc nitrate hexahydrate, the cobalt salt is cobalt nitrate hexahydrate, and the iron salt is ferric nitrate nonahydrate.
As a further improvement of the present invention, the molar ratio of the 2-methylimidazole to the zinc salt is 1.5 to 2.5: 1. further, the molar ratio of the 2-methylimidazole to the zinc salt is 2.1: 1.
As a further improvement of the invention, in step S4, the temperature of the water bath is 50-70 ℃, and the time of the water bath is 1-4 h; stirring time at room temperature is 6-14h, and stirring speed is 650 rpm.
As a further improvement of the invention, in step S4, the rotation speed of centrifugal separation is 6000-10000rpm, and washing is carried out for at least 2 times by using deionized water; the temperature of vacuum drying is 60-80 ℃, and the drying time is 10-14 h.
As a further improvement of the invention, in step S5, the calcination is performed in an inert gas atmosphere, the calcination temperature is 800-1000 ℃, and the calcination time is 1-3 h.
The invention also discloses a binary CoFe alloy loaded g-C3N4Catalyst, g-C supported by binary CoFe alloy as described in any one of above3N4The catalyst is prepared by the preparation method.
The invention also discloses the binary CoFe alloy loaded g-C3N4Use of a catalyst as a catalyst in a zinc air cell.
Compared with the prior art, the invention has the beneficial effects that:
the technical scheme of the invention adopts a one-pot method to synthesize Co/CoFe-NC @ g-C from bottom to top3N4Materials obtained with a porous two-dimensional g-C with abundant N coordination sites3N4The material is taken as a substrate, is beneficial to the uniform distribution growth of nano-scale Co nano-particles and CoFe alloy, and is compatible with commercial Pt/C and RuO2Compared with the prior art, the catalyst has good catalytic activity, stability and durability; the method has the advantages of simple preparation process, rich and controllable raw materials and higher large-scale production value.
Drawings
FIG. 1 is a schematic diagram of the preparation process of example 3 of the present invention.
FIG. 2 is an X-ray diffraction chart of the products obtained in example 1, example 2 and example 3 of the present invention.
Fig. 3 is a raman chart of products obtained in examples 1, 2, and 3 of the present invention.
FIG. 4 shows Co/CoFe-NC @ g-C obtained in example 3 of the present invention3N4Scanning electron micrograph (c).
FIG. 5 shows Co/CoFe-NC @ g-C obtained in example 3 of the present invention3N4Transmission electron micrograph (D).
FIG. 6 is a graph comparing oxygen reduction polarization curves of the catalysts prepared in examples 1, 2 and 3 of the present invention and commercial Pt/C.
FIG. 7 is a graph comparing the oxygen reduction stability cyclic voltammograms of the catalyst prepared in example 3 of the present invention with commercial Pt/C.
FIG. 8 shows the catalysts and commercial RuO prepared in examples 1, 2 and 3 of the present invention2Comparative graph of oxygen evolution polarization curve.
FIG. 9 shows the catalyst prepared in example 3 of the present invention and commercial RuO2Oxygen evolution stability cyclic voltammogram.
FIG. 10 shows the catalyst prepared in example 3 of the present invention and commercial Pt/C + RuO2Cycling stability test plots for assembled zinc-air cells.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below by way of examples. 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 ZIF-derived binary CoFe alloy loaded g-C3N4The preparation method of the bifunctional catalyst comprises the following steps:
step S1, synthesizing sheet-shaped two-dimensional porous g-C3N4: 10g of melamine was placed in an alumina crucible with a lid, heated in a muffle furnace at 550 ℃ for 2 h and 500 ℃ for 2 h, at a temperature rise rate of 5 ℃/min, and dispersed in 15ml of deionized water.
Step S2, 15 mmol of zinc nitrate hexahydrate, 15 mmol of cobalt nitrate hexahydrate, and a certain mass of ferric nitrate nonahydrate were dispersed in 120 ml of deionized water.
In step S3, 32 mmol of 2-methylimidazole and 0.5 g of polyvinylpyrrolidone were dispersed in 80 ml of deionized water.
Step S4, mixing the solutions of step S1, step S2 and step S3 at 60 degreeWater bath is carried out for 3 hours, stirring is carried out for 12 hours at room temperature, and the stirring speed is 650 rpm; the rotational speed of centrifugal separation is 8000 rpm, and deionized water is adopted for washing three times; the resulting product CoFe @ g-C3N4Vacuum drying at 60 deg.C for 12 h.
Step S5, obtaining CoFe @ g-C3N4Calcining in a tubular furnace to obtain g-C3N4Supported Co/CoFe-NC @ g-C3N4Material, maintenance of N during calcination2And (3) atmosphere, wherein the calcining temperature is 900 ℃, the calcining time is 2 h, and the heating rate is 5 ℃/min.
The invention is further illustrated by the following specific examples using the above preparation methods.
Example 1
The preparation of the Co-NC material comprises the following steps: (1) synthesis of Co-ZIF
4.462 g of zinc nitrate hexahydrate and 4.365 g of cobalt nitrate hexahydrate were dissolved in 120 mL of deionized water to form a clear solution. Meanwhile, 2.624 g of 2-methylimidazole and 0.5 g of polyvinylpyrrolidone were dissolved in another 80 mL of deionized water to form a clear solution, and finally the two solutions were mixed well, bathed in water at 60 ℃ for 3h, and stirred at 650 rpm for 12 h at room temperature. The product is washed three times by deionized water and dried for 12 h in vacuum at 60 ℃, and is marked as Co-ZIF.
(2) Synthesis of Co-NC
Weighing a proper amount of the product, placing the product in a tube furnace, heating to 900 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen, and keeping for 2 hours to obtain a final sample, and recording the final sample as Co-NC.
Example 2
The preparation of the Co/CoFe-NC material adopts the following steps:
(1) synthesis of CoFe-ZIF
4.462 g of zinc nitrate hexahydrate, 4.365 g of cobalt nitrate hexahydrate and 0.101 g of iron nitrate nonahydrate were dissolved in 120 mL of deionized water to form a clear solution. Meanwhile, 2.624 g of 2-methylimidazole and 0.5 g of polyvinylpyrrolidone were dissolved in another 80 mL of deionized water to form a clear solution, and finally the two solutions were mixed well, bathed in water at 60 ℃ for 3h, and stirred at 650 rpm for 12 h at room temperature. The product is washed three times by deionized water and dried for 12 h in vacuum at 60 ℃, and is marked as CoFe-ZIF.
(2) Synthesis of Co/CoFe-NC
Weighing a proper amount of the product, placing the product in a tube furnace, heating to 900 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen, and keeping for 2 hours to obtain a final sample, and recording the final sample as Co/CoFe-NC.
Example 3
Co/CoFe-NC@g-C3N4As shown in fig. 1, comprising the following steps:
（1）g-C3N4synthesis of (2)
10g of melamine is placed in an alumina crucible with a cover, and is heated in a muffle furnace at 550 ℃ for 2 h and 500 ℃ for 2 h in sequence, wherein the heating rate is 5 ℃/min, and g-C is obtained3N4Dispersed in 15ml of deionized water.
（2）CoFe@g-C3N4Synthesis of (2)
4.462 g of zinc nitrate hexahydrate, 4.365 g of cobalt nitrate hexahydrate and 0.101 g of iron nitrate nonahydrate were dissolved in 120 mL of deionized water to form a clear solution. Meanwhile, 2.624 g of 2-methylimidazole and 0.5 g of polyvinylpyrrolidone were dissolved in another 80 mL of deionized water to form a clear solution, and finally the two solutions were mixed well with the solution in step one, and the mixture was stirred at 650 rpm for 3h in a water bath at 60 ℃ for 12 h at room temperature. The product is washed three times by deionized water and dried for 12 h in vacuum at 60 ℃ and is marked as CoFe @ g-C3N4。
（3）Co/CoFe-NC@g-C3N4Synthesis of (2)
Weighing a proper amount of the product, placing the product in a tube furnace, heating to 900 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen, and keeping for 2 hours to obtain a final sample, and marking as Co/CoFe-NC @ g-C3N4。
The X-ray diffraction patterns of the catalyst products obtained in examples 1 to 3 are shown in FIG. 2, the Raman patterns of the catalyst products obtained in examples 1 to 3 are shown in FIG. 3, and the Co/CoFe-NC @ g-C obtained in example 33N4The scanning electron micrograph of (A) is shown in FIG. 4, and the transmission electron micrograph is shown in FIG. 5Shown in the figure.
The properties of the catalytic materials prepared in the above examples were tested.
Electrochemical testing was performed using a three-electrode system, with the counter electrode being a platinum plate, the reference electrode being an Ag/AgCl electrode, and the working electrode being a catalyst-coated glassy carbon electrode, where the catalyst was examples 1-3 and the commercial catalysts were Pt/C and RuO2. Both ORR and OER were tested using 0.1M aqueous KOH, but ORR requires an electrolyte that is saturated with oxygen. The preparation steps of the catalyst thin layer on the electrode are as follows: adding 300 muL of ethanol and 100 muL of Nafion solution (0.5 wt.%) into 4 mg of catalyst, ultrasonically dispersing for 30 min, dropping 4 muL of uniformly dispersed suspension liquid onto a smooth glassy carbon electrode by using a 10 muL liquid transfer gun, and testing after infrared drying, wherein the test result of electrochemical performance is shown in FIGS. 6-9.
From the ORR plots obtained for the different catalysts in oxygen-saturated 0.1M KOH solutions of FIG. 6, it can be seen that: of the four catalysts comprising commercial Pt/C, the catalyst Co/CoFe-NC @ g-C3N4Exhibits an optimum ORR performance, a half-wave potential of 0.87V and a potential of 5.90 mA cm-2The current density is limited by diffusion, exceeding that of the commercial 20% Pt/C catalyst (half-wave potential of 0.85V). Compared with Co @ NC, after a small amount of Fe is doped in Co, the Co/CoFe @ NC has better ORR performance, which proves that the added Fe element promotes the formation of bimetallic electronic synergistic effect of Co and Fe, thereby improving the ORR performance. Additionally, Co/CoFe @ g-C compares to Co/CoFe @ NC3N4Better ORR performance was obtained, confirming g-C3N4The key optimization function of (1).
As can be seen in FIG. 7, the catalyst Co/CoFe @ g-C was obtained after 2000 cycles under the same conditions3N4The potential shift of (A) is only 3 mV, whereas the commercial Pt/C is about 12 mV, which indicates that the electrode material Co/CoFe @ g-C is present under alkaline conditions3N4Has better ORR stability than the commercial Pt/C catalyst.
As can be seen from the OER plots obtained for the different catalysts of FIG. 8 in an oxygen-saturated 0.1M KOH solution: in the field of including commercial RuO2In the case of the four catalysts of (1),catalyst Co/CoFe-NC @ g-C3N4Shows an optimum OER performance at a current density of 10 mA cm-2The potential required by time potential water oxidation is 1.64V, which far exceeds the commercial RuO2Catalyst (potential 1.69V).
Fig. 9 and 10 are related performance tests of the catalyst prepared in example 3. FIG. 9 is the Co/CoFe-NC @ g-C obtained in example 33N4Catalyst and commercial RuO2FIG. 9 shows the comparison of cyclic voltammograms for stability to oxygen evolution, Co/CoFe @ g-C after 2000 CV cycles3N4The decay of the OER potential is only 2 mV, while RuO2The attenuation of (a) reached 14 mV, which means that Co/CoFe @ g-C3N4Has excellent OER stability.
Due to Co/CoFe @ g-C3N4Has excellent ORR and OER dual-functional catalytic activity, and can be used as cathode material for assembling rechargeable zinc-air battery. The performance test of the zinc-air battery is evaluated by a self-made battery, and the electrolyte is formed by mixing 6 mol of KOH electrolyte and 0.2 mol of zinc acetate solution. Specifically, the method comprises the steps of taking a polished zinc plate (with the thickness of 0.08 mm) as an anode, taking a carbon cloth modified by a catalyst as a cathode, and taking the active area of the cathode as-1 cm2. Experimental comparative catalysts were prepared from commercial Pt/C and RuO2(mass ratio =1: 1). The zinc-air battery test adopts a circulating constant current pulse method at 5 mA cm-2Is subjected to 5 minute galvanostatic discharge and charge cycles.
The catalyst prepared in example 3 was assembled into a zinc-air cell for open circuit voltage measurement based on Co/CoFe @ g-C3N4The open circuit potential of the assembled cell was 1.505V, which is at a high level in other non-noble metal catalysts.
FIG. 10 shows the catalyst prepared in example 3 and commercial Pt/C + RuO2The cycle stability test chart of the assembled zinc-air battery shows that the battery can maintain about 110 h (660 charge/discharge cycles), while the commercial Pt/C + RuO battery2It can only be maintained for 14h (about 84 charge/discharge cycles), which indicates that Co/CoFe @ g-C3N4Has excellent battery cycling stability. From the above experimental results, we believe to be based on Co/CoFe @ g-C3N4The zinc-air battery of the catalyst has great commercial potential even exceeding the current commercial catalyst Pt/C + RuO2。
Example 3 Co/CoFe-NC @ g-C compared to other materials3N4The material applied to the zinc-air battery is characterized in that: the evaporation of zinc metal creates more channels, exposing more active sites to the material; flake g-C3N4The carrier is provided with abundant N coordination sites, so that a substrate is provided for uniform distribution of Co/CoFe nanoparticles; the electrochemical performance of the material is further improved by the synergistic effect of the cobalt and iron double-element metal. In addition, the cobalt iron particles coated by the carbon layer can effectively inhibit corrosion and further improve the catalytic stability of the material. The material is modified on a glassy carbon electrode, and through cyclic voltammetry and linear scanning voltammetry tests, the half-wave potential of oxygen reduction of the optimal material is 0.87V, and oxygen is precipitated at the current density of 10 mA cm−2The lower voltage is 1.64V, which is respectively superior to the catalytic activity and durability of commercial platinum/carbon and ruthenium oxide catalysts, and has good application prospect. In addition, the optimal materials are assembled into the liquid zinc-air battery, and the circular charging performance and the power density are both excellent.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (8)
1. Binary CoFe alloy loaded g-C3N4The preparation method of the catalyst is characterized by comprising the following steps:
step S1, synthesizing sheet-shaped two-dimensional porous g-C3N4And dispersed in deionized water;
step S2, respectively dispersing zinc salt, cobalt salt and iron salt in deionized water;
step S3, dispersing 2-methylimidazole and polyvinylpyrrolidone in deionized water;
step S4, mixing the solutions obtained in the steps S1, S2 and S3, performing water bath reaction and stirring at room temperature, centrifuging, and performing vacuum drying to obtain a precursor;
step S5, placing the obtained precursor in a tube furnace to be calcined to obtain g-C3N4Supported Co/CoFe-NC @ g-C3N4A material;
in step S2, the molar ratio of zinc salt to cobalt salt is 1: 0.8-1.2;
the molar ratio of the 2-methylimidazole to the zinc salt is 1.5-2.5: 1.
2. the binary CoFe alloy loaded g-C of claim 13N4A method for producing a catalyst, characterized in that, in step S1, the sheet-like two-dimensional porous g-C3N4The preparation method comprises the following steps: placing melamine in a crucible, heating at 550 deg.C for 2 h in a muffle furnace, and heating at 500 deg.C for 2 h to obtain sheet-like porous g-C3N4A material.
3. The binary CoFe alloy loaded g-C of claim 13N4The preparation method of the catalyst is characterized by comprising the following steps: in step S2, the zinc salt is zinc nitrate hexahydrate, the cobalt salt is cobalt nitrate hexahydrate, and the iron salt is ferric nitrate nonahydrate.
4. The binary CoFe alloy loaded g-C of claim 13N4The preparation method of the catalyst is characterized by comprising the following steps: in the step S4, the temperature of the water bath is 50-70 ℃, and the time of the water bath is 1-4 h; stirring time at room temperature is 6-14h, and stirring speed is 650 rpm.
5. The binary CoFe alloy loaded g-C of claim 43N4Process for the preparation of a catalystCharacterized in that: in step S4, the rotation speed of centrifugal separation is 6000-10000rpm, and deionized water is adopted for washing at least 2 times; the temperature of vacuum drying is 60-80 ℃, and the drying time is 10-14 h.
6. The binary CoFe alloy of any of claims 1 to 5 loaded with g-C3N4The preparation method of the catalyst is characterized by comprising the following steps: in the step S5, the calcination is performed in an inert gas atmosphere at a temperature of 800-1000 ℃ for 1-3 h.
7. Binary CoFe alloy loaded g-C3N4A catalyst, characterized by: the method of any one of claims 1 to 6 is adopted to load g-C with the binary CoFe alloy3N4The catalyst is prepared by the preparation method.
8. The binary CoFe alloy loaded g-C of claim 73N4The application of the catalyst is characterized in that: it is used as a catalyst in zinc-air batteries.
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