CN108940336B - Nitrogen-doped cobalt-based carbon nano catalyst and preparation method and application thereof - Google Patents
Nitrogen-doped cobalt-based carbon nano catalyst and preparation method and application thereof Download PDFInfo
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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Abstract
The invention discloses a nitrogen-doped cobalt-based carbon nano catalyst, and a preparation method and application thereof. The invention firstly synthesizes Co (tzbc)2(H2O)4And then, taking the complex as a precursor, carrying out a carbonization reaction on the synthesized complex by a Chemical Vapor Deposition (CVD) method under an argon atmosphere, and naturally cooling to room temperature to obtain the nitrogen-doped cobalt-based carbon nano material. The preparation method is simple in preparation process, the preparation of the nitrogen-doped cobalt-based carbon nano material can be completed only by a CVD (chemical vapor deposition) furnace and without special atmosphere and pressure environment, the prepared nitrogen-doped cobalt-based carbon nano material contains graphitized carbon, cobalt nanocrystals and nitrogen doping, and meanwhile, the prepared nitrogen-doped cobalt-based carbon nano material has electro-catalytic hydrogen evolution and oxygen evolution activity and stability.
Description
Technical Field
The invention relates to a nitrogen-doped cobalt-based carbon nano catalyst, a preparation method and application thereof, and particularly relates to a method for preparing a nitrogen-doped cobalt-based carbon nano catalyst by taking a triazole-cobalt complex as a precursor and application thereof in the field of electrochemistry. Belonging to the field of novel material preparation and electrochemistry.
Background
At present, fossil energy such as coal, petroleum, natural gas and the like is the most important energy consumption main body in the current society, but the problems of reduced reserves, difficult exploitation and high production cost are faced. Therefore, for the sustainable development of human beings, it is very important to develop a new energy storage and conversion device which is low in cost, high in efficiency and easy to produce in large scale. Water electrolysis is an efficient and clean technique that can produce high purity hydrogen. It consists of two half-reactions: hydrogen Evolution Reaction (HER) on the cathode to produce H2Oxygen Evolution Reaction (OER) at the anode to produce O2. For the catalysts of HER and OER, it is of utmost importance to have high catalytic activity and stability resistance. Despite the noble metals (Pt) and noble metal oxides (RuO)2And IrO2) Are currently the most effective catalysts for HER and OER promotion, but their large-scale use is severely hampered by the expense and scarcity of such catalysts. Recently, transition metals (e.g., Fe, Co, Ni) that are abundant, have nanometer dimensions, and are low cost, are considered to be the most promising catalysts to replace precious metals and be applied to HER and OER. However, these non-noble metals are only stable over a narrow pH range, thereby limiting their use in a wide range of electrolytes. To solve this problem, a series of carbon-based transition metal composites having high durability in acidic and basic media have been intensively studied, particularly carbon-based materials in which transition metal nanoparticles are coated. Such coated materials may inhibit particle aggregation and avoid direct contact of the active substance with the electrolyte solution, thereby exhibiting unique stability. Thus, there is a need to obtain more efficient, stable transition metal nanoparticles coated in carbon materials and that can be used for electro-hydrolysis over a wide PH range.
The metal organic material with organic ligand and metal ion can be used as an ideal precursor to prepare uniformly dispersed nano carbon composite material by pyrolysis. Particularly for nitrogen-containing organic ligands, nitrogen doping can be realized without adding additional nitrogen sources and carrying out complex reaction, so that carbon materials generate defects, the conductivity of carbon is improved, and HER and OER reactions are facilitated. Yamauchi et Al summarize the use of metal-organic complexes as precursors for the electrochemical field, such as ZIF-67, MOF-5, Al-PCP, ZIF-8, ZIF-11, ZIF-67, IRMOFs, MIL-53, etc. (Y.V. Kaneti, Y.Yamauchi, et Al. adv. Mater., 2017, 29: 1604898). In contrast, complexes having a mononuclear structure are easily obtained by simple reactions and can be synthesized on a large scale. Furthermore, most mononuclear complexes are currently used mainly for single-crystal to single-crystal conversion, for example Cu (tzbc)2(H2O)4The use of complexes (m.m. Liu, x.m. Zhang, et al, Dalton trains, 2015, 44: 19796) is relatively limited. Therefore, it is promising to select a suitable nitrogen-containing mononuclear complex to obtain an N-doped transition metal carbon-based composite for HER and OER applications.
Disclosure of Invention
The invention aims to provide a nitrogen-doped cobalt-based carbon nano catalyst, and a preparation method and application thereof.
The invention provides a catalyst for a hydrogen evolution reaction and an oxygen evolution reaction, which is used for preparing a nitrogen-doped cobalt-based carbon nano material by using a triazole-cobalt complex as a precursor. In the invention, the complex is used as a precursor to ensure atomic contact in the reaction process, so that the uniformly dispersed catalyst is obtained, and the technical problems of complex preparation process, long period and high cost of the existing electrocatalyst are solved. The graphitized carbon layer generated by the invention can provide a conductive effect, and the coated cobalt nanoparticles can improve the catalytic activity and stability of the carbon layer.
The invention provides a nitrogen-doped cobalt-based carbon nano catalyst, which is prepared from mononuclear Co (tzbc)2(H2O)4The complex is used as a precursor, and the nitrogen-doped cobalt-based carbon nano material is synthesized in one step by a Chemical Vapor Deposition (CVD) method without adding an N source, and has a stable structural morphology.
The nitrogen-doped cobalt-based carbon nano catalyst comprises the following components in parts by weight:
nitrogen source: 16-18 parts of carbon source: 42-44 parts of cobalt source: 10-12 parts of oxygen source: 24-26 parts, hydrogen: 3-5 parts;
the nitrogen source, the cobalt source and the carbon source are derived from Co (tzbc)2(H2O)4And (3) a complex.
In the preparation method, the mononuclear Co (tzbc) is synthesized firstly2(H2O)4The complex contains Co, C and N, and then is carbonized by a CVD method in one step to synthesize the cobalt-based carbon nano material doped with nitrogen.
The invention provides a preparation method of the nitrogen-doped cobalt-based carbon nano catalyst, which comprises the following steps:
（1）Co(tzbc)2(H2O)4preparation of the complex: 4- (1H-1,2, 4-triazol-1-yl) benzoic acid (tzbc) and Co (NO)3)2·6H2Dissolving O in absolute ethyl alcohol and H with the volume ratio of 2: 1-4: 32Mixing with O in a magnetic stirrer, transferring the solution into a reaction kettle, and packaging at 130 deg.CoHeating at the temperature of C, taking out, and slowly cooling to room temperature in the air; then filtering, washing the product with ethanol to obtain light orange blocky crystals;
the 4- (1H-1,2, 4-triazol-1-yl) benzoic acid and Co (NO)3)2·6H2The mass ratio of O is 0.018-0.047: 0.059-0.148;
(2) CVD carbonization reaction: and (2) placing the complex obtained in the step (1) in the center of a quartz tube, setting the furnace temperature at 800 ℃, introducing inert gas as protective gas, carrying out carbonization reaction under the total gas pressure of 0.26-0.4 kPa for 2-6h, and then naturally cooling to room temperature under the argon atmosphere to obtain the nitrogen-doped cobalt-based carbon nano material.
In the preparation method, the inert gas is argon, and the temperature is uniformly raised to 800 ℃ in the presence of the argonoAnd C, performing chemical vapor deposition for 2-6 h.
The invention provides application of the nitrogen-doped cobalt-based carbon nano catalyst as an electrocatalyst in an electrocatalytic hydrogen evolution reaction and an electrocatalytic oxygen evolution reaction.
The application comprises the following steps: performing electrochemical measurement on an electrochemical workstation by using a three-electrode system; dispersing a catalyst containing 38-42 parts of catalyst and 6-10 parts of 5 wt% Nafion solution in a water/ethanol mixed solution with a volume ratio of 4:1, and then carrying out water bath ultrasonic treatment until a uniform catalyst suspension is formed; then 5 mul of the catalyst suspension was loaded onto a glassy carbon electrode with a diameter of 3 mm; the electrodes were dried at room temperature for 24h before measurement.
In the application, the carrying capacity of the catalyst can reach 285 mu g/cm2。
The invention has the beneficial effects that:
1) the preparation method has the characteristics of simple synthesis process, short preparation period and high efficiency; the nitrogen-doped cobalt-based carbon nano material is synthesized in one step only by the synthesized complex in an inert atmosphere (argon) through a Chemical Vapor Deposition (CVD) method, so that the preparation cost is greatly reduced;
2) the nitrogen-doped cobalt-based carbon nano material prepared by the process is characterized in that a wrapped metal Co nano crystal is embedded in a nitrogen-doped graphitized carbon layer (Co @ NC), and X-ray powder diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) show that the material contains Co, C, N and O elements; the morphology of a Transmission Electron Microscope (TEM) shows that the generated cobalt nanocrystals have high crystallization degree, and the fluffy graphitized layer is also beneficial to electron conduction.
3) The nitrogen-doped cobalt-based carbon nanomaterial prepared by the process has electrocatalytic hydrogen evolution and oxygen evolution catalytic performances, namely high activity, low initial potential, high current density, small Tafel slope, stable performance and the like.
Drawings
FIG. 1 is an XRD pattern of nitrogen-doped cobalt-based carbon nanomaterial prepared in example 1;
FIG. 2 is an SEM image of nitrogen-doped cobalt-based carbon nanomaterial prepared in example 2;
FIG. 3 is a TEM image of nitrogen-doped cobalt-based carbon nanomaterial prepared in example 3;
fig. 4 is a TEM image of nitrogen-containing doped cobalt-based carbon nanomaterial prepared in example 4 at high resolution;
fig. 5 is an XPS chart of nitrogen-doped cobalt-based carbon nanomaterial prepared in example 4, wherein fig. 5a is an XPS survey scan of example 4, fig. 5b is a C element scan of example 4, fig. 5C is an N element scan, and fig. 5d is a Co element scan;
FIG. 6 is a graph of a polarization curve and a graph of b taffeta when the material prepared by the invention is applied to electrochemical hydrogen evolution reaction, and the scanning rate is 50 mV/s;
FIG. 7 is a graph of a polarization curve and a graph of b Taffenbe curve of the material prepared by the present invention applied to electrochemical oxygen evolution reaction, and the scanning rate is 5 mV/s;
FIG. 8 is a graph showing the preparation of 1.0M KOH solution and 0.5M H, respectively, under hydrogen saturation in accordance with the present invention2SO4Chronoamperometric profile of hydrogen evolution reaction in solution.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present 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. In addition, the technical features involved in the different embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1
The embodiment provides a preparation method of a cobalt-based carbon nanomaterial doped with nitrogen, which is obtained by the following preparation steps:
(1) 4- (1H-1,2, 4-triazol-1-yl) benzoic acid (tzbc) (0.018 g, 0.1 mmol) and Co (NO)3)2·6H2O (0.059 g, 0.2 mmol) was dissolved in absolute ethanol (4 ml) and H2O (2 ml) in a mixed solvent, on a magnetic stirrer for about twenty minutes;
(2) the solution was transferred to a 15 ml reaction kettle and packaged at 130 deg.CoHeating and maintaining for 2 days at C, taking out, slowly cooling to room temperature in air, and standingFiltering to obtain orange blocky crystals;
(3) CVD carbonization reaction: the flow rate of argon gas was 100 sccm, the pressure was 0.3 Kpa, and the temperature of the CVD furnace was 800oAnd C, placing the triazole-cobalt complex prepared in the step (2) in the center of a quartz tube, carrying out carbonization reaction for 2 hours, and then naturally cooling to room temperature under the condition of keeping argon atmosphere to obtain the nitrogen-doped cobalt-based carbon nano material.
As shown in figure 1, in order that the XRD pattern of the material corresponds to the (002) diffraction peak of graphite carbon (JCPDS No. 13-0148) and the crystal faces of (111), (200) and (220) of simple substance Co (JCPDS No.15-0806) in a standard card library, the prepared nitrogen-doped cobalt-based carbon nano material does not contain other mixed phases except graphitized carbon and cobalt nano crystals, wherein the graphitized carbon and cobalt nano crystals are both from complex Co (tzbc)2(H2O)4。
Example 2
The embodiment provides preparation of a cobalt-based carbon nanomaterial doped with nitrogen, which is obtained by the following preparation steps:
(1) 4- (1H-1,2, 4-triazol-1-yl) benzoic acid (tzbc) (0.038 g, 0.2 mmol) and Co (NO)3)2·6H2O (0.119 g, 0.4 mmol) was dissolved in absolute ethanol (4 ml) and H2O (3 ml) in a mixed solvent, on a magnetic stirrer for about twenty minutes;
(2) the solution was transferred to a 15 ml reaction kettle and packaged at 130 deg.CoHeating and keeping for 2 days under C, then taking out and slowly cooling to room temperature in the air, and filtering to obtain orange blocky crystals;
(3) CVD carbonization reaction: the flow rate of argon gas was 100 sccm, the pressure was 0.32 Kpa, and the temperature of the CVD furnace was 800oAnd C, placing the triazole-cobalt complex prepared in the step (2) in the center of a quartz tube, carrying out carbonization reaction for 4 hours, and then naturally cooling to room temperature under the condition of keeping argon atmosphere to obtain the nitrogen-doped cobalt-based carbon nano material.
As shown in fig. 2, which is an SEM topography of the nitrogen-doped carbon nanomaterial prepared by the present invention, it can be seen that a carbon layer with a graphitized morphology is loaded with a plurality of dispersed Co nanoparticles.
Example 3
The embodiment provides preparation of a cobalt-based carbon nanomaterial doped with nitrogen, which is obtained by the following preparation steps:
(1) 4- (1H-1,2, 4-triazol-1-yl) benzoic acid (tzbc) (0.047 g, 0.25 mmol) and Co (NO)3)2·6H2O (0.148 g, 0.50 mmol) was dissolved in absolute ethanol (4 ml) and H2O (2.5 ml) in a mixed solvent, on a magnetic stirrer for about twenty minutes;
(2) the solution was transferred to a 15 ml reaction kettle and packaged at 130 deg.CoHeating and keeping for 2 days under C, then taking out and slowly cooling to room temperature in the air, and filtering to obtain orange blocky crystals;
(3) CVD carbonization reaction: the flow rate of argon gas was 100 sccm, the pressure was 0.4 Kpa, and the temperature of the CVD furnace was 800oAnd C, placing the triazole-cobalt complex prepared in the step (2) in the center of a quartz tube, carrying out carbonization reaction for 6 hours, and then naturally cooling to room temperature under the condition of keeping argon atmosphere to obtain the nitrogen-doped cobalt-based carbon nano material.
As shown in fig. 3, which is a TEM topography of the cobalt-based carbon nanomaterial containing nitrogen doping prepared by the present invention, it can be seen that the cobalt-based carbon nanomaterial containing nitrogen doping is composed of a two-dimensional graphitized carbon layer and surface-coated metallic Co nanoparticles.
Example 4
The embodiment provides preparation of a cobalt-based carbon nanomaterial doped with nitrogen, which is obtained by the following preparation steps:
(1) 4- (1H-1,2, 4-triazol-1-yl) benzoic acid (tzbc) (0.028 g, 0.15 mmol) and Co (NO)3)2·6H2O (0.095 g, 0.32 mmol) was dissolved in absolute ethanol (4 ml) and H2O (2.5 ml) in a mixed solvent, on a magnetic stirrer for about twenty minutes;
(2) the solution was transferred to a 15 ml reaction kettle and packaged at 130 deg.CoHeating and maintaining for 2 days under C, taking out, slowly cooling to room temperature in air, and filtering to obtain orange blockA crystalline form;
(3) CVD carbonization reaction: the flow rate of argon gas was 100 sccm, the pressure was 0.26 Kpa, and the temperature of the CVD furnace was 800oAnd C, placing the triazole-cobalt complex prepared in the step (2) in the center of a quartz tube, carrying out carbonization reaction for 3 hours, and then naturally cooling to room temperature under the condition of keeping argon atmosphere to obtain the nitrogen-doped cobalt-based carbon nano material.
As shown in fig. 4, which is a TEM topography of the cobalt-based carbon nanomaterial doped with nitrogen and prepared by the present invention under different resolutions, it can be seen that the lattice spacing of the cobalt nanoparticles in the sample is 0.205 nm, which belongs to the (111) crystal face of cubic metallic Co, which is consistent with the XRD result, indicating that the Co nanoparticles have high crystallinity; the spacing between carbon layers is 0.35 nm, is larger than the interlayer spacing (0.34 nm) of graphene, and belongs to a graphitized carbon layer structure.
As shown in fig. 5, an XPS spectrum of the nitrogen-doped cobalt-based carbon nanomaterial prepared by the present invention is shown, and fig. 5a is an XPS full spectrum scan of the nitrogen-doped cobalt-based carbon nanomaterial, which indicates that the nitrogen-doped cobalt-based carbon nanomaterial contains Co, N, C, and O, and all come from decomposition of the triazole-cobalt complex; FIG. 5b is a C element scan showing that the material contains carbon; FIG. 5c is a N-element scan showing that nitrogen-doped cobalt-based carbon nanomaterials comprise nitrogen-doped carbon nanomaterials; fig. 5d is a scanning diagram of Co element, which shows that the nitrogen-doped cobalt-based carbon nanomaterial contains cobalt nanoparticles.
Example 5: applications of
The application of the cobalt-based carbon nanomaterial doped with nitrogen as an electrocatalyst in an electrocatalytic hydrogen evolution reaction comprises the following steps:
electrochemical measurements were performed on an electrochemical workstation (CHI 660E) using a three electrode system. The nitrogen-doped cobalt-based carbon nanomaterial obtained in example 4 and a 5 wt% Nafion solution were dispersed in 1 mL of v/v 4:1 water/ethanol at a mass ratio of 40:8, followed by water bath sonication until a uniform suspension was formed. Then 5. mu.L of the catalyst suspension was loaded onto a glassy carbon electrode (diameter 3 mm). The electrodes were dried at room temperature for 24h before measurement. Catalyst supportThe loading capacity was 285. mu.g/cm2。
Hydrogen Evolution Reaction (HER) test:
at H2Saturated 0.5M H2SO4(pH = 0.3) in electrolyte solution, with platinum wire (CHI 115) as counter electrode, Hg/Hg of KCl solution was saturated2Cl2Electrode as reference electrode and inventive preparation example 4 as working electrode a three electrode system was formed to test HER performance. Linear Sweep Voltammetry (LSV) at a sweep rate of 50 mV s-1The test was performed. All potentials were exchanged for a standard hydrogen electrode (RHE): e (rhe) = e (sce) + (0.242 + 0.059 pH). As shown in FIG. 6a, which is a polarization curve, it can be seen that the cobalt-based carbon nanomaterial catalyst doped with nitrogen has a current density of 10 mA.cm-2The overpotential was 122 mV. As shown in FIG. 6b, which is a Tafel plot, it can be seen that this material has a lower Tafel slope, about 54 mV dec-1。
Oxygen Evolution Reaction (OER) test:
at O2Saturated 1.0M KOH (pH = 14) electrolyte solution with platinum wire (CHI 115) as counter electrode, saturated KCl solution Hg/Hg2Cl2The electrode was used as a reference electrode and example 4, prepared in accordance with the invention, was used as a working electrode to form a three-electrode system for testing oxygen evolution reactions. The scan rate of the polarization curve is 5 mV s-1. All potentials were converted to standard hydrogen electrodes (RHE). As shown in FIG. 7a, which is a polarization curve of example 3, it can be seen that at a current density of 10 mA cm-2The overpotential is 365 mV, as shown in FIG. 7b, which is a Tafel plot, it can be seen that the material prepared by the present invention has a low Tafel slope, about 130 mV dec-1。
And (3) stability testing: as shown in FIG. 8, the nitrogen-doped cobalt-based carbon nanomaterial prepared by the method is 0.5M H saturated in hydrogen2SO4Chronoamperometric profile in solution and in 1M KOH solution saturated with oxygen. As can be seen from FIG. 8, the cobalt-based carbon nanomaterial doped with nitrogen prepared by the invention has almost no attenuation of polarization current compared with the initial value after 100000 s test at constant potential, and shows good effectStability of (2).
Claims (6)
1. A cobalt-based carbon nanocatalyst doped with nitrogen, which is characterized in that: with single-core Co (tzbc)2(H2O)4The complex is used as a precursor, and under the condition that an N source is not required to be added, the nitrogen-doped cobalt-based carbon nanomaterial is synthesized in one step by a chemical vapor deposition method, and has a stable structural morphology;
the preparation method of the nitrogen-doped cobalt-based carbon nano catalyst comprises the following steps:
（1）Co(tzbc)2(H2O)4preparation of the complex:
mixing 4- (1H-1,2, 4-triazole-1-yl) benzoic acid and Co (NO)3)2·6H2O is dissolved in absolute ethanol and H2Mixing with O in a magnetic stirrer, transferring the solution into a reaction kettle, and packaging at 130 deg.CoHeating at the temperature of C, taking out, and slowly cooling to room temperature in the air; then filtering, washing the product with ethanol to obtain orange blocky crystals;
the 4- (1H-1,2, 4-triazol-1-yl) benzoic acid and Co (NO)3)2·6H2The mass ratio of O is 0.018-0.047: 0.059-0.148;
(2) CVD carbonization reaction: and (2) placing the complex obtained in the step (1) in the center of a quartz tube, setting the furnace temperature at 800 ℃, introducing inert gas as protective gas, carrying out carbonization reaction under the total gas pressure of 0.26-0.4 kPa, and then naturally cooling to room temperature under the inert atmosphere to obtain the nitrogen-doped cobalt-based carbon nano catalyst.
2. The nitrogen-doped cobalt-based carbon nanocatalyst of claim 1, wherein: absolute ethyl alcohol and H in the mixed solvent in the step (1)2The volume ratio of O is 2: 1-4: 3.
3. The nitrogen-doped cobalt-based carbon nanocatalyst of claim 1, wherein: the inert gas is argon, and the temperature is raised at a constant speed in the presence of the argonTo 800oAnd C, performing chemical vapor deposition for 2-6 h.
4. Use of the nitrogen-doped cobalt-based carbon nanocatalyst of claim 1 as an electrocatalyst for electrocatalytic hydrogen evolution reactions and electrocatalytic oxygen evolution reactions.
5. Use according to claim 4, characterized in that it comprises the following steps: performing electrochemical measurement on an electrochemical workstation by using a three-electrode system; dispersing a catalyst containing 38-42 parts of catalyst and 6-10 parts of 5 wt% Nafion solution in a water/ethanol mixed solution with a volume ratio of 4:1, and then carrying out water bath ultrasonic treatment until a uniform catalyst suspension is formed; then 5 mul of the catalyst suspension was loaded onto a glassy carbon electrode with a diameter of 3 mm; the electrodes were dried at room temperature for 24h before measurement.
6. Use according to claim 5, characterized in that: the carrying capacity of the catalyst can reach 285 mu g/cm2。
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