CN112758902A - Optimized electronic configuration Co for efficient oxygen evolution reaction4Preparation method of N nanosheet - Google Patents
Optimized electronic configuration Co for efficient oxygen evolution reaction4Preparation method of N nanosheet Download PDFInfo
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- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/0615—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with transition metals other than titanium, zirconium or hafnium
- C01B21/0622—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with transition metals other than titanium, zirconium or hafnium with iron, cobalt or nickel
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Abstract
The invention discloses an optimized electronic configuration Co for efficient oxygen evolution reaction4A method of making N nanoplates, comprising: synthesis of Co (CO)3)0.5(OH)·0.11H2An O nanosheet precursor; synthesis of Co3O4Nanosheet precursor: mixing Co (CO)3)0.5(OH)·0.11H2Calcining the O nanosheet precursor in air atmosphere, and cooling to room temperature to obtain Co3O4A precursor; synthesis of Co4N nanosheet: calcination of Co in Ammonia atmosphere3O4Precursor to obtain Co4N nanosheets; regulating Co4Electronic configuration of N nanoplate: by mixing in argon and hydrogenCalcining Co in a closed atmosphere4N nanosheet to adjust Co4The nitrogen content of the N nanosheet, so that the purpose of regulating and controlling the electronic configuration of Co is achieved. By the invention to Co4Partial reduction is carried out on the N nano sheet to obtain defective Co with different nitrogen contents4N nano-sheet. Defective Co with different nitrogen contents4N nanosheets have different electronic configurations, with e of Co ionsgThe electronic filling number is also different, and the method has great use potential in the fields of catalysis, energy storage and the like.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to an optimized electronic configuration Co for high-efficiency oxygen evolution reaction4A preparation method of N nano-sheets.
Background
As an important anode reaction, electrochemical Oxidation (OER) plays a semi-reactive role in many energy conversion processes, such as water decomposition, carbon dioxide reduction, and rechargeable metal-air batteries. The OER process suffers from slow kinetics due to the participation of multi-step proton coupled electron transfer, which drives the development of highly efficient catalysts. RuO2And IrO2Are two highly active OER electrocatalysts, but their high cost and low inventory limit large scale applications. Therefore, researchers are looking for transition metal compounds as non-noble metal substitutes, such as oxides, hydroxides, sulfides, selenides, phosphides, and nitrides.
In recent years, cobalt nitride (Co)4N) is receiving increasing attention due to its metalloid nature and favorable electronic conductivity. Derived from oxides or hydroxides, Co4N has oxidized Co on the surface as OERThe active site of (1). Various Co-based materials have been tried by many research groups4N nanomaterials were successfully developed as OER catalysts. In these Co4In N nanomaterials, the surface cobalt oxide active sites typically exhibit a +3 valence. Usually Co3+The ion exhibits t in the low spin state2g 6eg 0Exhibits t in the high spin state2g 4eg 2The electronic configuration of (a). But according to Shao-Horn's theory, the best egThe number of electrons is 1.2, this is in contrast to Co4Co in N3+E of the active sitegThe electrons are different. Therefore, it is necessary to regulate Co4Electronic configuration of N to manipulate e of Co active sitegNumber of filling, thereby increasing Co4Intrinsic activity of the N catalyst.
Disclosure of Invention
An object of the present invention is to solve at least the above problems and/or disadvantages and to provide at least the advantages described hereinafter.
To achieve these objects and other advantages in accordance with the present invention, an optimized electron configuration Co for high efficiency oxygen evolution reactions is provided4The preparation method of the N nanosheet comprises the following steps:
step one, synthesizing Co (CO)3)0.5(OH).0.11H2O nanosheet precursor: adding cobalt acetylacetonate and hexadecyl trimethyl ammonium bromide into a mixed solvent of ethylene glycol and deionized water, stirring for 15-30 min to obtain a mixed solution, transferring the mixed solution into a high-pressure reaction kettle, sealing, heating at 175-185 ℃ for 45-50 h, naturally cooling to room temperature, centrifuging and collecting the obtained precipitate, washing with water and absolute ethyl alcohol for three times respectively, and vacuum drying at 55-65 ℃ for 12-24 h to obtain Co (CO)3)0.5(OH).0.11H2An O nanosheet precursor;
step two, synthesizing Co3O4Nanosheet precursor: mixing Co (CO)3)0.5(OH).0.11H2Calcining the O nanosheet precursor for 3-8 minutes at 300-350 ℃ in air atmosphere, and cooling to room temperature to obtain the O nanosheetCo3O4A precursor;
step three, synthesizing Co4N nanosheet: heating to 450-550 ℃ at a heating rate of 3-6 ℃/min in an ammonia atmosphere to calcine Co3O4Precursor is used for 1.5-2.5 hours to obtain Co4N nanosheets;
step four, regulating and controlling Co4Electronic configuration of N nanoplate: by calcining Co in a mixed atmosphere of argon and hydrogen4N nanosheet to adjust Co4The nitrogen content of the N nanosheet, so that the purpose of regulating and controlling the electronic configuration of Co is achieved.
Preferably, in the first step, the volume ratio of the ethylene glycol to the deionized water is 5-6: 1; the mass volume ratio of the cobalt acetylacetonate to the mixed solvent is 0.6g: 60-80 mL; the mass ratio of the cobalt acetylacetonate to the hexadecyl trimethyl ammonium bromide is 1: 3-5;
preferably, in the fourth step, the calcining temperature is 500-600 ℃, and the heating rate is 3-6 ℃/min; the calcination time is 1-3 hours.
Preferably, in the first step, before the mixed solution is transferred into the high-pressure reaction kettle, an Nd: YAG pulse laser is used for carrying out ultraviolet pulse laser irradiation on the mixed solution.
Preferably, the mixed solution is irradiated by ultraviolet pulse laser for 30-45 min; the wavelength of the ultraviolet pulse laser irradiation is 355nm, the pulse width is 10-20 ns, and the pulse frequency is 10-30 Hz; the single pulse energy is 25-120 mJ.
Preferably, in the first step, the obtained Co (CO) is3)0.5(OH).0.11H2Adding the O nanosheet precursor and water into a supercritical device, soaking for 30-60 min in a supercritical water system with the temperature of 375-395 ℃ and the pressure of 20-25 MPa, and filtering to obtain pretreated Co (CO)3)0.5(OH).0.11H2And (3) O nanosheet precursor.
Preferably, the Co (CO)3)0.5(OH).0.11H2The mass ratio of the O nanosheet precursor to the water is 1: 25-50.
It is preferable that the first and second liquid crystal layers are formed of,in the second step, low-temperature plasma is adopted to carry out the treatment on Co3O4And treating the precursor for 120-150 s.
Preferably, the atmosphere of the low-temperature plasma processor is nitrogen and/or ammonia; the frequency of the low-temperature plasma treatment instrument is 30-55 KHz, the power is 80-120W, and the pressure of the atmosphere is 20-30 Pa.
The invention at least comprises the following beneficial effects: the invention aims to overcome Co4The existing problems of low catalytic activity, poor stability and the like of the N nanosheet, and provides a preparation method of the cobalt nitride nanosheet with the optimized electronic configuration, high catalytic activity and high stability. The invention firstly prepares Co by a hydrothermal method3O4The nanosheet precursor is subjected to high-temperature nitridation to synthesize Co4N nano-sheet. By the pair of Co4Partial reduction is carried out on the N nano sheet to obtain defective Co with different nitrogen contents4N nano-sheet. Defective Co with different nitrogen contents4N nanosheets have different electronic configurations, with e of Co ionsgThe electronic filling number is also different, and the method has great use potential in the fields of catalysis, energy storage and the like.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Description of the drawings:
FIG. 1 shows an optimized electronic configuration Co prepared in example 1 of the present invention4TEM images of N nanoplates;
FIG. 2 shows an optimized electronic configuration Co prepared in example 2 of the present invention4TEM images of N nanoplates;
FIG. 3 shows an optimized electronic configuration Co prepared in example 3 of the present invention4TEM images of N nanoplates;
FIG. 4 shows the optimized electronic configuration Co prepared in comparative example 1 of the present invention4TEM images of N nanoplates;
FIG. 5 shows Co prepared in examples 1 to 3 of the present invention and comparative example 14XRD pattern of N nano sheet;
FIG. 6 shows Co prepared in examples 1 to 3 of the present invention and comparative example 14Of N nanosheetsPolarization curves of electrochemical experiments;
FIG. 7 shows Co prepared in examples 1 and 4 of the present invention4Polarization curve of electrochemical experiment of N nanometer slice;
FIG. 8 shows Co prepared in examples 1 and 5 of the present invention4Polarization curve of electrochemical experiment of N nanometer slice;
FIG. 9 shows Co prepared in examples 1 and 6 of the present invention4Polarization curve of electrochemical experiment of N nanometer slice;
FIG. 10 shows Co prepared in examples 1 and 7 of the present invention4Polarization curve of electrochemical experiment of N nanosheet.
The specific implementation mode is as follows:
the present invention is further described in detail below with reference to the attached drawings so that those skilled in the art can implement the invention by referring to the description text.
It will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
Example 1:
optimized electronic configuration Co for efficient oxygen evolution reaction4The preparation method of the N nanosheet comprises the following steps:
step one, synthesizing Co (CO)3)0.5(OH).0.11H2O nanosheet precursor: adding 600 mg of cobalt acetylacetonate and 2.2 g of hexadecyl trimethyl ammonium bromide into a mixed solvent of 60 ml of ethylene glycol and 11 ml of deionized water, stirring for 20min to obtain a mixed solution, transferring the mixed solution into a 100 ml high-pressure reaction kettle, sealing, heating at 180 ℃ for 48 hours, naturally cooling to room temperature, centrifuging and collecting the obtained precipitate, washing with water and absolute ethyl alcohol for three times respectively, and drying in vacuum at 60 ℃ for 24 hours to obtain Co (CO)3)0.5(OH).0.11H2An O nanosheet precursor;
step two, synthesizing Co3O4Nanosheet precursor: mixing Co (CO)3)0.5(OH).0.11H2O nanosheet precursor in the airCalcining at 320 ℃ for 5 minutes in an air atmosphere, and cooling to room temperature to obtain Co3O4A precursor;
step three, synthesizing Co4N nanosheet: in the atmosphere of ammonia gas, the temperature is raised to 500 ℃ at the temperature rise speed of 5 ℃/min to calcine Co3O4Precursor for 2 hours to obtain Co4N nanosheets;
step four, regulating and controlling Co4Electronic configuration of N nanoplate: by calcining Co in a mixed atmosphere of argon and hydrogen4Calcining the N nanosheets at 550 ℃ and at a heating rate of 5 ℃/min; the calcination time is 1 hour; obtaining optimized electronic configuration Co4N nanosheets; calculated the Co4E of N nanosheetsgNumber of electron fillings: 1.03.
example 2:
optimized electronic configuration Co for efficient oxygen evolution reaction4The preparation method of the N nanosheet comprises the following steps:
step one, synthesizing Co (CO)3)0.5(OH).0.11H2O nanosheet precursor: adding 600 mg of cobalt acetylacetonate and 2.2 g of hexadecyl trimethyl ammonium bromide into a mixed solvent of 60 ml of ethylene glycol and 11 ml of deionized water, stirring for 20min to obtain a mixed solution, transferring the mixed solution into a 100 ml high-pressure reaction kettle, sealing, heating at 180 ℃ for 48 hours, naturally cooling to room temperature, centrifuging and collecting the obtained precipitate, washing with water and absolute ethyl alcohol for three times respectively, and drying in vacuum at 60 ℃ for 24 hours to obtain Co (CO)3)0.5(OH).0.11H2An O nanosheet precursor;
step two, synthesizing Co3O4Nanosheet precursor: mixing Co (CO)3)0.5(OH).0.11H2Calcining the O nano sheet precursor for 5 minutes at 320 ℃ in air atmosphere, and cooling to room temperature to obtain Co3O4A precursor;
step three, synthesizing Co4N nanosheet: in the atmosphere of ammonia gas, the temperature is raised to 500 ℃ at the temperature rise speed of 5 ℃/min to calcine Co3O4Precursor for 2 hours to obtain Co4N nanosheets;
step four, regulating and controlling Co4Electronic configuration of N nanoplate: by calcining Co in a mixed atmosphere of argon and hydrogen4Calcining the N nanosheets at 550 ℃ and at a heating rate of 5 ℃/min; the calcination time is 2 hours; obtaining optimized electronic configuration Co4N nanosheets; calculated the Co4E of N nanosheetsgNumber of electron fillings: 1.18.
example 3:
optimized electronic configuration Co for efficient oxygen evolution reaction4The preparation method of the N nanosheet comprises the following steps:
step one, synthesizing Co (CO)3)0.5(OH).0.11H2O nanosheet precursor: adding 600 mg of cobalt acetylacetonate and 2.2 g of hexadecyl trimethyl ammonium bromide into a mixed solvent of 60 ml of ethylene glycol and 11 ml of deionized water, stirring for 20min to obtain a mixed solution, transferring the mixed solution into a 100 ml high-pressure reaction kettle, sealing, heating at 180 ℃ for 48 hours, naturally cooling to room temperature, centrifuging and collecting the obtained precipitate, washing with water and absolute ethyl alcohol for three times respectively, and drying in vacuum at 60 ℃ for 24 hours to obtain Co (CO)3)0.5(OH).0.11H2An O nanosheet precursor;
step two, synthesizing Co3O4Nanosheet precursor: mixing Co (CO)3)0.5(OH).0.11H2Calcining the O nano sheet precursor for 5 minutes at 320 ℃ in air atmosphere, and cooling to room temperature to obtain Co3O4A precursor;
step three, synthesizing Co4N nanosheet: in the atmosphere of ammonia gas, the temperature is raised to 500 ℃ at the temperature rise speed of 5 ℃/min to calcine Co3O4Precursor for 2 hours to obtain Co4N nanosheets;
step four, regulating and controlling Co4Electronic configuration of N nanoplate: by calcining Co in a mixed atmosphere of argon and hydrogen4Calcining the N nanosheets at 550 ℃ and at a heating rate of 5 ℃/min; the calcination time is 2 hours; obtaining optimized electronic configuration Co4N nanosheets; calculated the Co4E of N nanosheetsgNumber of electron fillings: 1.33.
example 4:
optimized electronic configuration Co for efficient oxygen evolution reaction4The preparation method of the N nanosheet comprises the following steps:
step one, synthesizing Co (CO)3)0.5(OH).0.11H2O nanosheet precursor: adding 600 mg of cobalt acetylacetonate and 2.2 g of hexadecyl trimethyl ammonium bromide into a mixed solvent of 60 ml of ethylene glycol and 11 ml of deionized water, stirring for 20min to obtain a mixed solution, and performing ultraviolet pulse laser irradiation on the mixed solution for 30min by using an Nd: YAG pulse laser; then transferring the mixed solution into a 100 ml high-pressure reaction kettle, sealing, heating at 180 ℃ for 48 hours, naturally cooling to room temperature, centrifuging and collecting the obtained precipitate, washing with water and absolute ethyl alcohol for three times respectively, and vacuum drying at 60 ℃ for 24 hours to obtain Co (CO)3)0.5(OH).0.11H2An O nanosheet precursor; the wavelength of the ultraviolet pulse laser irradiation is 355nm, the pulse width is 15ns, and the pulse frequency is 15 Hz; the single pulse energy is 80 mJ; the reactants are completely dissolved by ultraviolet pulse laser irradiation, and a stable mixed solution is formed, which is beneficial to the hydrothermal reaction;
step two, synthesizing Co3O4Nanosheet precursor: mixing Co (CO)3)0.5(OH).0.11H2Calcining the O nano sheet precursor for 5 minutes at 320 ℃ in air atmosphere, and cooling to room temperature to obtain Co3O4A precursor;
step three, synthesizing Co4N nanosheet: in the atmosphere of ammonia gas, the temperature is raised to 500 ℃ at the temperature rise speed of 5 ℃/min to calcine Co3O4Precursor for 2 hours to obtain Co4N nanosheets;
step four, regulating and controlling Co4Electronic configuration of N nanoplate: by calcining Co in a mixed atmosphere of argon and hydrogen4Calcining the N nanosheets at 550 ℃ and at a heating rate of 5 ℃/min; the calcination time is 1 hour; obtaining optimized electronic configuration Co4N nanosheets; calculated the Co4E of N nanosheetsgNumber of electron fillings: 1.111.
example 5:
optimized electronic configuration Co for efficient oxygen evolution reaction4The preparation method of the N nanosheet comprises the following steps:
step one, synthesizing Co (CO)3)0.5(OH).0.11H2O nanosheet precursor: adding 600 mg of cobalt acetylacetonate and 2.2 g of hexadecyl trimethyl ammonium bromide into a mixed solvent of 60 ml of ethylene glycol and 11 ml of deionized water, stirring for 20min to obtain a mixed solution, transferring the mixed solution into a 100 ml high-pressure reaction kettle, sealing, heating at 180 ℃ for 48 hours, naturally cooling to room temperature, centrifuging and collecting the obtained precipitate, washing with water and absolute ethyl alcohol for three times respectively, and drying in vacuum at 60 ℃ for 24 hours to obtain Co (CO)3)0.5(OH).0.11H2An O nanosheet precursor; mixing Co (CO)3)0.5(OH).0.11H2Adding an O nanosheet precursor and water into a supercritical device, soaking for 30-60 min in a supercritical water system with the temperature of 380 ℃ and the pressure of 25MPa, and filtering to obtain pretreated Co (CO)3)0.5(OH).0.11H2An O nanosheet precursor; the Co (CO)3)0.5(OH).0.11H2The mass ratio of the O nanosheet precursor to the water is 1: 30;
step two, synthesizing Co3O4Nanosheet precursor: mixing Co (CO)3)0.5(OH).0.11H2Calcining the O nano sheet precursor for 5 minutes at 320 ℃ in air atmosphere, and cooling to room temperature to obtain Co3O4A precursor;
step three, synthesizing Co4N nanosheet: in the atmosphere of ammonia gas, the temperature is raised to 500 ℃ at the temperature rise speed of 5 ℃/min to calcine Co3O4Precursor for 2 hours to obtain Co4N nanosheets;
step four, regulating and controlling Co4Electronic configuration of N nanoplate: by calcining Co in a mixed atmosphere of argon and hydrogen4Calcining the N nanosheets at 550 ℃ and at a heating rate of 5 ℃/min; the calcination time is 1 hour;obtaining optimized electronic configuration Co4N nanosheets; calculated the Co4E of N nanosheetsgNumber of electron fillings: 1.14.
example 6:
optimized electronic configuration Co for efficient oxygen evolution reaction4The preparation method of the N nanosheet comprises the following steps:
step one, synthesizing Co (CO)3)0.5(OH).0.11H2O nanosheet precursor: adding 600 mg of cobalt acetylacetonate and 2.2 g of hexadecyl trimethyl ammonium bromide into a mixed solvent of 60 ml of ethylene glycol and 11 ml of deionized water, stirring for 20min to obtain a mixed solution, transferring the mixed solution into a 100 ml high-pressure reaction kettle, sealing, heating at 180 ℃ for 48 hours, naturally cooling to room temperature, centrifuging and collecting the obtained precipitate, washing with water and absolute ethyl alcohol for three times respectively, and drying in vacuum at 60 ℃ for 24 hours to obtain Co (CO)3)0.5(OH).0.11H2An O nanosheet precursor;
step two, synthesizing Co3O4Nanosheet precursor: mixing Co (CO)3)0.5(OH).0.11H2Calcining the O nano sheet precursor for 5 minutes at 320 ℃ in air atmosphere, and cooling to room temperature to obtain Co3O4A precursor; by using low-temperature plasma to Co3O4Treating the precursor for 150 s; the atmosphere of the low-temperature plasma treatment instrument is nitrogen; the frequency of the low-temperature plasma processor is 30KHz, the power is 120W, and the pressure of the atmosphere is 30 Pa;
step three, synthesizing Co4N nanosheet: in the atmosphere of ammonia gas, the temperature is raised to 500 ℃ at the temperature rise speed of 5 ℃/min to calcine Co3O4Precursor for 2 hours to obtain Co4N nanosheets;
step four, regulating and controlling Co4Electronic configuration of N nanoplate: by calcining Co in a mixed atmosphere of argon and hydrogen4Calcining the N nanosheets at 550 ℃ and at a heating rate of 5 ℃/min; the calcination time is 1 hour; obtaining optimized electronic configuration Co4N nanosheets; calculated the Co4E of N nanosheetsgNumber of electron fillings: 1.16.
example 7:
optimized electronic configuration Co for efficient oxygen evolution reaction4The preparation method of the N nanosheet comprises the following steps:
step one, synthesizing Co (CO)3)0.5(OH).0.11H2O nanosheet precursor: adding 600 mg of cobalt acetylacetonate and 2.2 g of hexadecyl trimethyl ammonium bromide into a mixed solvent of 60 ml of ethylene glycol and 11 ml of deionized water, stirring for 20min to obtain a mixed solution, and performing ultraviolet pulse laser irradiation on the mixed solution for 30min by using an Nd: YAG pulse laser; transferring the mixed solution into a 100 ml high-pressure reaction kettle, sealing, heating at 180 ℃ for 48 hours, naturally cooling to room temperature, centrifuging and collecting the obtained precipitate, washing with water and absolute ethyl alcohol respectively for three times, and vacuum drying at 60 ℃ for 24 hours to obtain Co (CO)3)0.5(OH).0.11H2An O nanosheet precursor; mixing Co (CO)3)0.5(OH).0.11H2Adding an O nanosheet precursor and water into a supercritical device, soaking for 30-60 min in a supercritical water system with the temperature of 380 ℃ and the pressure of 25MPa, and filtering to obtain pretreated Co (CO)3)0.5(OH).0.11H2An O nanosheet precursor; the Co (CO)3)0.5(OH).0.11H2The mass ratio of the O nanosheet precursor to the water is 1: 30; the wavelength of the ultraviolet pulse laser irradiation is 355nm, the pulse width is 15ns, and the pulse frequency is 15 Hz; the single pulse energy is 80 mJ;
step two, synthesizing Co3O4Nanosheet precursor: mixing Co (CO)3)0.5(OH).0.11H2Calcining the O nano sheet precursor for 5 minutes at 320 ℃ in air atmosphere, and cooling to room temperature to obtain Co3O4A precursor; by using low-temperature plasma to Co3O4Treating the precursor for 150 s; the atmosphere of the low-temperature plasma treatment instrument is nitrogen; the frequency of the low-temperature plasma processor is 30KHz, the power is 120W, and the pressure of the atmosphere is 30 Pa;
step three, synthesizing Co4N nanosheet: in the atmosphere of ammonia gas, the temperature is raised to 500 ℃ at the temperature rise speed of 5 ℃/min to calcine Co3O4Precursor for 2 hours to obtain Co4N nanosheets;
step four, regulating and controlling Co4Electronic configuration of N nanoplate: by calcining Co in a mixed atmosphere of argon and hydrogen4Calcining the N nanosheets at 550 ℃ and at a heating rate of 5 ℃/min; the calcination time is 1 hour; obtaining optimized electronic configuration Co4N nanosheets; calculated the Co4E of N nanosheetsgNumber of electron fillings: 1.19.
comparative example 1:
optimized electronic configuration Co for efficient oxygen evolution reaction4The preparation method of the N nanosheet comprises the following steps:
step one, synthesizing Co (CO)3)0.5(OH).0.11H2O nanosheet precursor: adding 600 mg of cobalt acetylacetonate and 2.2 g of hexadecyl trimethyl ammonium bromide into a mixed solvent of 60 ml of ethylene glycol and 11 ml of deionized water, stirring for 20min to obtain a mixed solution, transferring the mixed solution into a 100 ml high-pressure reaction kettle, sealing, heating at 180 ℃ for 48 hours, naturally cooling to room temperature, centrifuging and collecting the obtained precipitate, washing with water and absolute ethyl alcohol for three times respectively, and drying in vacuum at 60 ℃ for 24 hours to obtain Co (CO)3)0.5(OH).0.11H2An O nanosheet precursor;
step two, synthesizing Co3O4Nanosheet precursor: mixing Co (CO)3)0.5(OH).0.11H2Calcining the O nano sheet precursor for 5 minutes at 320 ℃ in air atmosphere, and cooling to room temperature to obtain Co3O4A precursor;
step three, synthesizing Co4N nanosheet: in the atmosphere of ammonia gas, the temperature is raised to 500 ℃ at the temperature rise speed of 5 ℃/min to calcine Co3O4Precursor for 2 hours to obtain Co4N nanosheets; calculated the Co4E of N nanosheetsgNumber of electron fillings: 0.83.
prepared as described in examples 1 to 7Co4And (3) carrying out electrochemical measurement on the N nanosheets: all electrochemical measurements were performed at room temperature and atmospheric pressure in a typical three-electrode system containing 40mL of O2Saturated 1M KOH electrolyte; the electrochemical measurements were carried out at an electrochemical workstation (CHI660E) in a three-electrode system; platinum wire and Hg/HgO electrodes are used as counter electrode and reference electrode respectively; to prepare the working electrode, 3mg of sample (Co prepared in examples 1-7) was sonicated for 4h4N nanoplatelets) and 30 μ l of an affion solution (5 wt%) were dispersed in 2mL of ethanol to form a homogeneous ink; the dispersion was then uniformly dispersed over an area of 1X 2cm2On carbon paper of (1); the prepared working electrode was dried under vacuum overnight for further use.
Obtaining a polarization curve by linear sweep voltammetry measurement at a sweep rate of 1 mV/s; polarization curves for examples 1-3 and comparative example 1 are shown in FIG. 6; polarization curves for examples 1 and 4-7 are shown in FIGS. 7-10;
at a current density of 10mA/cm2When the overpotential of the nanosheets prepared in example 1 is 245mV (the abscissa reading in the figure minus 1.23, i.e., E-1.23), the overpotential of the nanosheets prepared in example 2 is 190 mV; the overpotential of the nanosheets prepared in example 3 was 270 mV; the overpotential of the nanosheet prepared in comparative example 1 was 314 mV; the overpotential of the nanosheets prepared in example 4 was 235mV, and the overpotential of the nanosheets prepared in example 5 was 230 mV; the overpotential of the nanosheets prepared in example 6 was 200 mV; overpotential 185mV for nanoplatelets prepared in example 7; the low overpotential proves the high catalytic activity of the nanosheet on OER, and the lower the overpotential is, the smaller the applied voltage is in the reaction process, so that the energy is saved.
While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable in various fields of endeavor to which the invention pertains, and further modifications may readily be made by those skilled in the art, it being understood that the invention is not limited to the details shown and described herein without departing from the general concept defined by the appended claims and their equivalents.
Claims (9)
1. Optimized electronic configuration Co for efficient oxygen evolution reaction4The preparation method of the N nanosheet is characterized by comprising the following steps:
step one, synthesizing Co (CO)3)0.5(OH).0.11H2O nanosheet precursor: adding cobalt acetylacetonate and hexadecyl trimethyl ammonium bromide into a mixed solvent of ethylene glycol and deionized water, stirring for 15-30 min to obtain a mixed solution, transferring the mixed solution into a high-pressure reaction kettle, sealing, heating at 175-185 ℃ for 45-50 h, naturally cooling to room temperature, centrifuging and collecting the obtained precipitate, washing with water and absolute ethyl alcohol for three times respectively, and vacuum drying at 55-65 ℃ for 12-24 h to obtain Co (CO)3)0.5(OH).0.11H2An O nanosheet precursor;
step two, synthesizing Co3O4Nanosheet precursor: mixing Co (CO)3)0.5(OH).0.11H2Calcining the O nanosheet precursor for 3-8 minutes at 300-350 ℃ in air atmosphere, and cooling to room temperature to obtain Co3O4A precursor;
step three, synthesizing Co4N nanosheet: heating to 450-550 ℃ at a heating rate of 3-6 ℃/min in an ammonia atmosphere to calcine Co3O4Precursor is used for 1.5-2.5 hours to obtain Co4N nanosheets;
step four, regulating and controlling Co4Electronic configuration of N nanoplate: by calcining Co in a mixed atmosphere of argon and hydrogen4N nanosheet to adjust Co4The nitrogen content of the N nanosheet, so that the purpose of regulating and controlling the electronic configuration of Co is achieved.
2. Optimized electronic configuration Co for high efficiency oxygen evolution reaction according to claim 14The preparation method of the N nanosheet is characterized in that in the first step, the volume ratio of ethylene glycol to deionized water is 5-6: 1; the mass volume ratio of the cobalt acetylacetonate to the mixed solvent is 0.6g: 60-80 mL; of cobalt acetylacetonate and cetyltrimethylammonium bromideThe mass ratio is 1: 3-5;
3. optimized electronic configuration Co for high efficiency oxygen evolution reaction according to claim 14The preparation method of the N nanosheet is characterized in that in the fourth step, the calcining temperature is 500-600 ℃, and the heating rate is 3-6 ℃/min; the calcination time is 1-3 hours.
4. Optimized electronic configuration Co for high efficiency oxygen evolution reaction according to claim 14The preparation method of the N nanosheet is characterized in that in the first step, before the mixed solution is transferred into a high-pressure reaction kettle, an Nd-YAG pulse laser is used for carrying out ultraviolet pulse laser irradiation on the mixed solution.
5. Optimized electronic configuration Co for high efficiency oxygen evolution reaction according to claim 44The preparation method of the N nanosheet is characterized in that the mixed solution is irradiated by ultraviolet pulse laser for 30-45 min; the wavelength of the ultraviolet pulse laser irradiation is 355nm, the pulse width is 10-20 ns, and the pulse frequency is 10-30 Hz; the single pulse energy is 25-120 mJ.
6. Optimized electronic configuration Co for high efficiency oxygen evolution reaction according to claim 14The preparation method of the N nanosheet is characterized in that in the step one, the obtained Co (CO) is used3)0.5(OH).0.11H2Adding the O nanosheet precursor and water into a supercritical device, soaking for 30-60 min in a supercritical water system with the temperature of 375-395 ℃ and the pressure of 20-25 MPa, and filtering to obtain pretreated Co (CO)3)0.5(OH).0.11H2And (3) O nanosheet precursor.
7. Optimized electronic configuration Co for high efficiency oxygen evolution reaction according to claim 14Method for preparing N nanosheets, characterized in that the Co (CO)3)0.5(OH).0.11H2The mass ratio of the O nanosheet precursor to the water is 1: 25-50.
8. Optimized electronic configuration Co for high efficiency oxygen evolution reaction according to claim 14The preparation method of the N nanosheet is characterized in that in the second step, low-temperature plasma is adopted to carry out reaction on Co3O4And treating the precursor for 120-150 s.
9. Optimized electronic configuration Co for high efficiency oxygen evolution reaction according to claim 14The preparation method of the N nanosheet is characterized in that the atmosphere of the low-temperature plasma treatment instrument is nitrogen and/or ammonia; the frequency of the low-temperature plasma treatment instrument is 30-55 KHz, the power is 80-120W, and the pressure of the atmosphere is 20-30 Pa.
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| CN115624984A (en) * | 2022-09-26 | 2023-01-20 | 西北工业大学 | Transition metal doped Co 4 N nano combustion catalyst and preparation method thereof |
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