CN111001428B - A kind of metal-free carbon-based electrocatalyst and preparation method and application - Google Patents
A kind of metal-free carbon-based electrocatalyst and preparation method and application Download PDFInfo
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Abstract
本发明属于电化学和新能源领域，具体涉及一种无金属碳基电催化剂及制备方法和应用。本发明一种无金属氮掺杂碳基电催化材料的制备方法，利用两种有机配体作为氮源和碳源，在室温下通过一锅法反应合成金属有机骨架作为前驱体，进一步通过惰性气氛下高温热解合成出无金属碳基电催化材料。本发明可作为电催化剂在电化学析氢反应、析氧反应和氧还原反应中应用。也可应用于可充放电锌空气电池空气阴极。无金属碳基电催化剂拥有多催化活性位点，所制备的三功能催化材料拥有丰富的C‑Nx活性位点，分层多孔结构，与产生的石墨化碳层协同作用，提高电催化活性。同时无金属电催化剂制备工艺简单，原料价格低廉，适合大规模工业化生产。
The invention belongs to the fields of electrochemistry and new energy, and in particular relates to a metal-free carbon-based electrocatalyst, a preparation method and an application. The present invention is a method for preparing a metal-free nitrogen-doped carbon-based electrocatalytic material. Two organic ligands are used as nitrogen sources and carbon sources, and metal-organic frameworks are synthesized as precursors through a one-pot reaction at room temperature, and further through inert Metal-free carbon-based electrocatalytic materials were synthesized by high-temperature pyrolysis in an atmosphere. The invention can be used as an electrocatalyst in electrochemical hydrogen evolution reaction, oxygen evolution reaction and oxygen reduction reaction. It can also be applied to the air cathode of rechargeable zinc-air batteries. Metal-free carbon-based electrocatalysts possess multiple catalytically active sites, and the prepared trifunctional catalytic materials possess abundant C- Nx active sites, hierarchical porous structures, and synergize with the resulting graphitized carbon layers to enhance electrocatalytic activity . At the same time, the metal-free electrocatalyst has a simple preparation process and low cost of raw materials, and is suitable for large-scale industrial production.
Description
Technical Field
The invention belongs to the field of electrochemistry and new energy, and particularly relates to a metal-free carbon-based electrocatalyst, a preparation method and application thereof.
Background
At present, the world energy consumption is mainly mineral energy such as petroleum, coal, natural gas and the like, and the serious problem of energy exhaustion is also faced while the ecological environment is damaged. Energy conservation, emission reduction and energy transformation become the necessary ways for sustainable development of human beings. The search for efficient, green, sustainable and safe energy sources is becoming more and more urgent. The metal-air battery is a new-generation green secondary battery, has the advantages of low cost, no pollution, high specific power, high specific energy and the like, not only has rich resources, but also can be recycled, and hasHas good development and application prospect. In metal air batteries, the positive electrode reactions involve oxygen reduction (ORR) and Oxygen Evolution (OER) reactions during discharge and charge, respectively. Hydrogen production by water electrolysis is another efficient and clean energy technology, can produce hydrogen with high purity, and consists of two half reactions: hydrogen Evolution Reaction (HER) on the cathode to produce H2Oxygen Evolution Reaction (OER) at the anode to produce O2. In the current practical application, platinum-based catalysts are still high-efficiency catalysts for ORR/HER, while iridium-and ruthenium-based catalysts are excellent OER catalysts, however the disadvantages of high cost, scarcity of noble metals, poor long-term stability, susceptibility to poisoning, etc. severely limit the large-scale commercial application of these noble metal catalysts. Thus, over the last decade, there has been an effort to develop new highly efficient non-noble metal electrocatalysts that can be used to catalyze ORR, OER and HER.
Among various materials, a metal-free carbon-nitrogen co-doped material and a transition metal carbon-nitrogen co-doped material are considered to be promising candidate materials. It has been developed that the transition metal carbon nitrogen co-doped material can be prepared by high-temperature pyrolysis after the single precursors of metal, nitrogen and carbon are uniformly mixed. However, metal nanoparticles are easily agglomerated during pyrolysis, and a large amount of nitrogen source is lost, so that the density of catalytic active sites is reduced, the electrocatalytic performance is negatively affected, and the catalytic activity is reduced. Therefore, designing a metal-free carbon-nitrogen co-doped material becomes one of the current research hotspots. The currently reported metal-free electrocatalyst has good catalytic activity in the ORR, OER or HER reactions alone, partial performance exceeds that of a precious metal catalyst, however, the catalyst with three functions, namely good catalytic performance in the ORR, OER and HER reactions, is still rarely reported, and the cost of the three-function non-precious metal catalyst can be greatly reduced in the aspects of catalyst preparation and device preparation when the three-function non-precious metal catalyst is applied to fuel cells, metal air batteries and full water splitting devices.
Disclosure of Invention
Aiming at the problems that metal nano particles are easy to agglomerate and the density of catalytic active sites is low in the pyrolysis process of the conventional transition metal material, the invention provides a metal-free carbon-based electrocatalyst, and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a metal-free nitrogen-doped carbon-based electro-catalytic material comprises the following components: the content of C element is 90-92%, the content of N element is 4-5%, and the content of O element is 4-5%.
A preparation method of a metal-nitrogen-free doped carbon-based electro-catalytic material comprises the steps of utilizing two organic ligands as a nitrogen source and a carbon source, reacting at room temperature by a one-pot method to synthesize a metal organic framework as a precursor, and further performing high-temperature pyrolysis in an inert atmosphere to synthesize the metal-nitrogen-free carbon-based electro-catalytic material. The method has the advantages of simple and easily obtained raw materials, low cost and easy large-scale production, and the prepared material has high oxygen reduction performance and is equivalent to a noble metal Pt-based material.
The method comprises the following steps of utilizing two organic ligands as a nitrogen source and a carbon source, reacting and synthesizing a metal organic framework as a precursor by a one-pot method at room temperature, and further performing high-temperature pyrolysis under an inert atmosphere to synthesize the metal-free carbon-based electrocatalytic material, wherein the method specifically comprises the following steps:
Further, the preparation method of the methanol solution of the mixed ligand of benzimidazole and adenine in the step 1 specifically comprises the following steps: the benzimidazole and the adenine are simultaneously dissolved in a methanol solution according to the molar ratio of 1:1 to prepare the benzimidazole derivative.
Still further said Zn (NO)3)2The molar ratio of benzimidazole to adenine is 1:1: 1-0.8; said Zn (NO) is contained3)2The concentration of the DMF solution, the methanol solution containing benzimidazole and the methanol solution containing adenine is respectively 0.1mol/L, 0.05mol/L and 0.05-0.04 mol/L.
Further, in the step 1, the stirring time is 6 hours; in the step 2, the black product is soaked in the aqua regia for 6 hours; soaking in concentrated nitric acid at 70 ℃ for 12h in the step 2; in the step 2, the inert gas is nitrogen or argon, the temperature is raised to 200 ℃ at the heating rate of 2 ℃/min in the presence of the inert gas and then is kept for 2h, and then the temperature is raised to 950 ℃ at the heating rate of 3 ℃/min and the carbonization time is kept for 5 h.
An application of a metal-free nitrogen-doped carbon-based catalyst as an electrocatalyst in electrochemical hydrogen evolution reaction, oxygen evolution reaction and oxygen reduction reaction.
The application method of the metal-free nitrogen-doped carbon-based catalyst comprises the following steps: performing an electrochemical test on an electrochemical workstation by using a three-electrode system; dispersing 5mg of catalyst and 80. mu.L of 5% Nafion solution in 1mL of DMF, followed by ultrasonic treatment in a water bath until a uniform black suspension is formed; then 10 mul of black suspension is dripped on a glassy carbon electrode with the diameter of 5 mm; naturally drying the electrode at room temperature before measurement; the content of the catalyst is 0.25mg/cm2。
An application of a metal-free nitrogen-doped carbon-based catalyst is applied to an air cathode of a chargeable and dischargeable zinc-air battery.
An application method of a metal-free nitrogen-doped carbon-based catalyst comprises the steps of mixing a metal-free carbon-based catalyst C-ZN-50 with a dispersant and a binder, and performing ultrasonic dispersion to obtain slurry; uniformly dripping the slurry on the pretreated carbon paper, and drying to obtain the electrode slice;
the addition amount of the catalyst is 4-7 mg; the volume ratio of the dispersing agent to the binder is 1000: 80; the dispersant is DMF, and the binder is Nafion solution
Compared with the prior art, the invention has the following advantages:
1. the invention develops a method for taking a metal organic framework material as a precursor by taking two organic ligands as a carbon source and a nitrogen source, and the carbonized metal-free carbon-based electrocatalyst has multiple catalytic active sites and meets the requirements of a three-function catalyst.
2. The three-functional catalytic material prepared by the invention has rich C-NxThe active sites, the layered porous structure, and the generated graphitized carbon layer act synergistically to improve the electrocatalytic activity. Meanwhile, the metal-free electrocatalyst has simple preparation process and low raw material price, and is suitable for large-scale industrial production.
3. The catalytic material prepared by the invention has higher electro-catalytic activity and stability of oxygen reduction and hydrogen/oxygen precipitation under the alkaline condition, is applied to assembled zinc-air batteries and has the concentration of 10mA cm-2The next had a charge-discharge cycle of 145 hours.
Drawings
FIG. 1 is a comparison of a powder X-ray diffraction (PXRD) pattern of a one-pot synthetic ZN-50 and a single crystal fitted PXRD pattern;
FIG. 2 is a powder X-ray diffraction (PXRD) pattern of the C-ZN-50 electrocatalyst obtained after carbonization;
FIG. 3 is a scanning electron micrograph of a catalyst prepared according to the present invention;
FIG. 4a is a transmission electron micrograph at 100nm magnification of a catalyst prepared according to the present invention;
FIG. 4b is a transmission electron micrograph at 5nm magnification of the catalyst prepared according to the present invention;
FIG. 5a is a polarization diagram of a catalyst prepared according to the present invention and commercial Pt/C when applied to an electrochemical oxygen reduction reaction;
FIG. 5b is a Tafel plot of a catalyst prepared according to the present invention and commercial Pt/C when applied to an electrochemical oxygen reduction reaction;
FIG. 6a is a polarization curve of a catalyst prepared according to the present invention and commercial Pt/C when applied to an electrochemical hydrogen evolution reaction;
FIG. 6b is a Tafel plot of a catalyst prepared according to the present invention and commercial Pt/C when applied to an electrochemical hydrogen evolution reaction;
FIG. 7a shows a RuO and catalyst prepared according to the present invention2A polarization curve chart applied to electrochemical oxygen evolution reaction;
FIG. 7b shows RuO and catalyst prepared according to the present invention2A tafel plot applied to electrochemical oxygen evolution reaction;
fig. 8 is a schematic view of a zinc-air cell device;
FIG. 9 is a graph showing the discharge polarization curve and power density curve of a zinc-air battery assembled by using the catalyst prepared by the invention as a positive electrode material;
fig. 10 shows the charge and discharge performance test of the zinc-air battery assembled by using the catalyst prepared by the invention as the anode material, wherein each pulse time is 10 min.
In FIG. 8, 1-zinc plate (negative), 2-C-ZN-50 (positive), 3-electrolyte, 4-gas diffusion layer, 5-oxygen.
Detailed Description
The technical solution of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are some embodiments of the present invention.
Example 1
The embodiment provides a preparation method of a metal-free carbon-based electrocatalyst, which is obtained by the following preparation steps:
preparation of ZN-50 precursor: zinc nitrate hexahydrate (Zn (NO)3)2·6H2O) (5mmol) was dissolved in 50mL of DMF solution, benzimidazole (5mmol) and adenine (5mmol) were dissolved in 100mL of methanol solution, and Zn (NO) was added while stirring3)2The DMF solution of (A) was quickly added to a methanol solution containing benzimidazole and adenine. Reacting for 6h at room temperature, centrifuging, collecting precipitate, and vacuum drying at 60 deg.C to obtain white powder.
Preparation of C-ZN-50 electrocatalyst: and (2) putting the ZN-50 prepared in the step (1) into the center of a tube furnace, heating to 200 ℃ at a heating rate of 2 ℃/min under a nitrogen atmosphere, keeping for 2 hours, heating to 950 ℃ at a heating rate of 3 ℃/min, keeping for 5 hours, and naturally cooling to room temperature to obtain black powder. Soaking the obtained black product in aqua regia for 6 hours, washing the black product to be neutral by deionized water, then soaking the black product in concentrated nitric acid at 70 ℃ for 12 hours, washing the black product to be neutral by the deionized water, and drying the black product in vacuum to obtain the metal-free carbon-based C-ZN-50 catalyst.
Example 2
The embodiment provides a preparation method of a metal-free carbon-based electrocatalyst, which is obtained by the following preparation steps:
(1) preparation of ZN-50 precursor: zinc nitrate hexahydrate (Zn (NO)3)2·6H2O) (5mmol) was dissolved in 50mL of DMF solution, benzimidazole (5mmol) and adenine (4mmol) were dissolved in 100mL of methanol solution, and Zn (NO) was added while stirring3)2The DMF solution of (A) was quickly added to a methanol solution containing benzimidazole and adenine. Reacting for 6h at room temperature, centrifuging, collecting precipitate, and vacuum drying at 60 deg.C to obtain white powder.
(2) Preparation of C-ZN-50 electrocatalyst: and (2) putting the ZN-50 prepared in the step (1) into the center of a tube furnace, heating to 200 ℃ at a heating rate of 2 ℃/min under a nitrogen atmosphere, keeping for 2 hours, heating to 950 ℃ at a heating rate of 3 ℃/min, keeping for 5 hours, and naturally cooling to room temperature to obtain black powder. Soaking the obtained black product in aqua regia for 6 hours, washing the black product to be neutral by deionized water, then soaking the black product in concentrated nitric acid at 70 ℃ for 12 hours, washing the black product to be neutral by the deionized water, and drying the black product in vacuum to obtain the metal-free carbon-based C-ZN-50 catalyst.
Example 3
The embodiment provides a preparation method of a metal-free carbon-based electrocatalyst, which is obtained by the following preparation steps:
(1) preparation of ZN-50 precursor: zinc nitrate hexahydrate (Zn (NO)3)2·6H2O) (5mmol) was dissolved in 50mL of DMF solution, benzimidazole (5mmol) and adenine (4.5mmol) were dissolved in 100mL of methanol solution, and Zn (NO) was contained while stirring3)2The DMF solution is quickly added to the methanol solution containing benzimidazole and adenineIn the liquid. Reacting for 6h at room temperature, centrifuging, collecting precipitate, and vacuum drying at 60 ℃ to obtain white powder ZN-50.
(2) Preparation of C-ZN-50 electrocatalyst: and (2) putting the ZN-50 prepared in the step (1) into the center of a tube furnace, heating to 200 ℃ at a heating rate of 2 ℃/min under a nitrogen atmosphere, keeping for 2 hours, heating to 950 ℃ at a heating rate of 3 ℃/min, keeping for 5 hours, and naturally cooling to room temperature to obtain black powder. Soaking the obtained black product in aqua regia for 6 hours, washing the black product to be neutral by deionized water, then soaking the black product in concentrated nitric acid at 70 ℃ for 12 hours, washing the black product to be neutral by the deionized water, and drying the black product in vacuum to obtain the metal-free carbon-based C-ZN-50 catalyst.
As shown in fig. 1, which is a PXRD pattern of ZN-50, it is shown that PXRD diffraction peaks of MOFs formed by assembling two organic ligands in zinc salt correspond to peaks fitted to single crystals, and that synthesized precursors are pure phase and have good crystallinity.
FIG. 2 shows a PXRD pattern of ZN-50 carbonized material C-ZN-50, in which diffraction peaks at 26 degrees and 44 degrees are obvious and can well correspond to (002) and (101) planes of graphitized carbon.
As shown in FIG. 3, which is an SEM image of a C-ZN-50 material, it can be seen that nanoparticles formed by the material are crosslinked to form a hierarchical porous structure.
As shown in fig. 4, which is a TEM image of the C-ZN-50 material, it can be seen that the hierarchical porous structure (a) formed by the material is formed, and it can be seen that the clear crystal lattice corresponds to the graphitized carbon (002) plane.
Example 4
And (3) electrochemical performance testing:
the prepared metal-free carbon-based material is used for ORR, HER and OER electrochemical performance tests.
Electrochemical tests were performed on an electrochemical workstation using a three electrode system, containing 5mg of catalyst and 80 μ L of 5% Nafion solution dispersed in 1mL DMF followed by water bath sonication until a homogeneous black suspension was formed; then 10 mul of black suspension is dripped on a glassy carbon electrode with the diameter of 5 mm; before measurement, the electrode is naturally dried at room temperature, and the content of the catalyst is 0.25mg/cm2(ii) a The working electrode is a modified glassy carbon electrode, the counter electrode is a platinum wire, the reference electrode is an Ag/AgCl electrode, and for HER and OER tests, a 1M potassium hydroxide solution is used as an electrolyte to perform linear voltammetry scanning at a scanning speed of 10 mV/s; the ORR test was performed using a 0.1M potassium hydroxide solution as electrolyte and a linear voltammetric sweep at a sweep rate of 5 mV/s.
FIG. 5a is a comparison of polarization curves of the catalytic Oxygen Reduction Reaction (ORR) of the catalyst obtained according to the present invention and a commercial Pt/C catalyst, showing that the half-wave potential of the ORR is 0.82V, which has superior catalytic performance over the commercial Pt/C catalyst; FIG. 5b is a Tafel plot of the resulting catalyst and a commercial Pt/C catalyst for the catalytic oxygen reduction (ORR), and it can be seen that the material prepared by the present invention has a very low Tafel slope, about 82mV/dec, which is lower than that of the commercial Pt/C catalyst.
FIG. 6a is a graph comparing the polarization curves of the catalyst obtained in the present invention and the commercial Pt/C catalyst for catalyzing the Hydrogen Evolution Reaction (HER), and it can be seen that the current density is 10mA/cm2The overpotential of the catalyst is 309mV, which shows that the catalyst has excellent catalytic effect; FIG. 6b is a Tafel plot of the resulting catalyst and a commercial Pt/C catalyst catalyzing the Hydrogen Evolution Reaction (HER), and it can be seen that the material prepared by the present invention has a lower Tafel slope of about 165 mV/dec.
FIG. 7a shows the catalyst and RuO obtained by the present invention2The polarization curves of the catalytic Oxygen Evolution Reaction (OER) of the catalyst are compared, and it can be seen that the current density is 10mA/cm2The overpotential is 560mV, which shows that the catalyst has better catalytic effect; FIG. 7b shows the resulting catalyst and RuO2The Tafel curve of catalytic Oxygen Evolution Reaction (OER) shows that the material prepared by the invention has lower Tafel slope which is about 349 mV/dec.
Example 5
The method is applied to an air cathode of a chargeable and dischargeable zinc-air battery, 4-7 mg of a metal-free carbon-based catalyst C-ZN-50 is mixed with DMF and Nafion, the volume ratio of the DMF to the Nafion is 1000:80, and slurry is obtained after ultrasonic dispersion; and uniformly dripping the slurry on the pretreated carbon paper, and drying to obtain the electrode slice.
Fig. 8 is a schematic view of a zinc-air cell device. The cathode is a zinc plate, and the anode is an air cathode sheet loaded with the catalyst prepared by the invention. The electrolyte is a mixed solution of 6mol/L potassium hydroxide and 0.2mol/L zinc acetate, and a gas phase diffusion layer is arranged on the surface of the anode, which is in contact with air.
FIG. 9 is a graph of the polarization discharge curve and corresponding power density curves for a zinc-air cell device assembled with the prepared catalyst at current densities of 10 and 100mA/cm-2When the voltage of the battery is 1.23V and 0.80V respectively, the maximum power density of the battery is 87mW/cm-2。
As shown in FIG. 10, the zinc-air battery assembled by the catalyst prepared by the invention has no obvious change in charge-discharge voltage difference after 145h of cyclic charge-discharge test, which shows that the prepared catalyst has very strong stability and higher practical application value.
In conclusion, the metal-free carbon-based C-ZN-50 catalyst obtained by the preparation method has catalytic activity of three reactions of ORR, HER and OER, and raw materials adopted in synthesis are cheap and easy to obtain, and the preparation process is simple and pollution-free.
The invention is not limited to the embodiments described above, but may be modified or varied by a person skilled in the art in light of the above description, all such modifications and variations being within the scope of the invention as defined by the appended claims.
Claims (5)
1. A preparation method of a metal-free nitrogen-doped carbon-based electro-catalysis material is characterized by comprising the following steps: the preparation method comprises the steps of utilizing two organic ligands of benzimidazole and adenine as a nitrogen source and a carbon source, reacting at room temperature by a one-pot method to synthesize a metal zinc organic framework as a precursor, further performing high-temperature pyrolysis under inert atmosphere and removing metal zinc, and synthesizing the metal-free carbon-based electro-catalytic material.
2. The method for preparing the metal nitrogen-doped carbon-based electrocatalytic material as claimed in claim 1, wherein the method comprises the following steps: the method comprises the following steps of utilizing two organic ligands as a nitrogen source and a carbon source, reacting and synthesizing a metal organic framework as a precursor by a one-pot method at room temperature, and further performing high-temperature pyrolysis under an inert atmosphere to synthesize the metal-free carbon-based electrocatalytic material, wherein the method specifically comprises the following steps:
step 1, preparation of ZN-50 precursor: will contain Zn (NO)3)2Quickly pouring the N, N-Dimethylformamide (DMF) solution into a methanol solution containing a mixed ligand of benzimidazole and adenine, stirring at room temperature, centrifuging, collecting precipitate, and drying overnight in vacuum to obtain white powder, namely a ZN-50 precursor;
step 2, preparation of C-ZN-50 electrocatalyst: and (2) putting the ZN-50 precursor into the center of a tubular furnace, setting the temperature of the tubular furnace at 950 ℃, introducing gas in an inert atmosphere for protection, naturally cooling to room temperature in the inert atmosphere after carbonization to obtain a black product, soaking the obtained black product in aqua regia, washing the black product to be neutral by deionized water, then soaking the black product in concentrated nitric acid to remove zinc ions possibly existing, washing the black product to be neutral by the deionized water, and drying in vacuum to obtain the metal-free carbon-based C-ZN-50 material, namely the metal-nitrogen-doped carbon-based electrocatalytic material.
3. The method for preparing the metal nitrogen-doped carbon-based electrocatalytic material as claimed in claim 2, wherein the method comprises the following steps: the preparation method of the methanol solution of the benzimidazole and adenine mixed ligand in the step 1 specifically comprises the following steps: the benzimidazole and the adenine are simultaneously dissolved in a methanol solution according to the molar ratio of 1:1 to prepare the benzimidazole derivative.
4. The method for preparing the metal nitrogen-doped carbon-based electrocatalytic material as claimed in claim 2, wherein the method comprises the following steps: the Zn (NO)3)2The molar ratio of benzimidazole to adenine is 1:1: 1-0.8; said Zn (NO) is contained3)2The concentrations of benzimidazole and adenine in the DMF solution and the methanol solution are respectively 0.1mol/L, 0.05mol/L and 0.05-0.04 mol/L.
5. The method for preparing the metal nitrogen-doped carbon-based electrocatalytic material as claimed in claim 2, wherein the method comprises the following steps: in the step 1, the stirring time is 6 hours; in the step 2, the black product is soaked in the aqua regia for 6 hours; soaking in concentrated nitric acid at 70 ℃ for 12h in the step 2; and 2, in the step 2, the gas in the inert atmosphere is nitrogen or argon, the temperature is raised to 200 ℃ at the temperature raising rate of 2 ℃/min in the presence of the gas in the inert atmosphere, the temperature is maintained for 2 hours, and the temperature is raised to 950 ℃ at the temperature raising rate of 3 ℃/min, and the carbonization time is maintained for 5 hours.
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