CN109759120B - Nitrogen and nickel co-doped cobalt selenide ultrathin nanosheet and preparation method and application thereof - Google Patents
Nitrogen and nickel co-doped cobalt selenide ultrathin nanosheet and preparation method and application thereof Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 230
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 218
- QVYIMIJFGKEJDW-UHFFFAOYSA-N cobalt(ii) selenide Chemical compound [Se]=[Co] QVYIMIJFGKEJDW-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 117
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 114
- 239000002135 nanosheet Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
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- 239000011669 selenium Substances 0.000 claims abstract description 47
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 32
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000005406 washing Methods 0.000 claims abstract description 28
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 27
- 239000010941 cobalt Substances 0.000 claims abstract description 27
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002243 precursor Substances 0.000 claims abstract description 20
- 238000004729 solvothermal method Methods 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 17
- 239000001257 hydrogen Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 8
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- 229940091258 selenium supplement Drugs 0.000 claims description 26
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical group O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 claims description 8
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- 229960001471 sodium selenite Drugs 0.000 claims description 8
- 235000015921 sodium selenite Nutrition 0.000 claims description 8
- 239000011781 sodium selenite Substances 0.000 claims description 8
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 6
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 6
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 229940078494 nickel acetate Drugs 0.000 claims description 4
- 150000002815 nickel Chemical group 0.000 claims 1
- 229910000510 noble metal Inorganic materials 0.000 abstract description 3
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 32
- 238000006243 chemical reaction Methods 0.000 description 24
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 238000003917 TEM image Methods 0.000 description 10
- 238000001878 scanning electron micrograph Methods 0.000 description 10
- HZUJFPFEXQTAEL-UHFFFAOYSA-N azanylidynenickel Chemical compound [N].[Ni] HZUJFPFEXQTAEL-UHFFFAOYSA-N 0.000 description 8
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
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- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
The invention provides nitrogen and nickel co-doped selenizationCobalt ultrathin nanosheets and a preparation method and application thereof, belonging to the technical field of catalysts for hydrogen production by water electrolysis. The preparation method provided by the invention comprises the following steps: (1) mixing a cobalt source, a selenium source, a nickel source, a nitrogen source, water and diethylenetriamine, and carrying out a solvothermal reaction to obtain a nitrogen and nickel co-doped cobalt selenide precursor; (2) and washing and drying the nitrogen and nickel co-doped cobalt selenide precursor to obtain the nitrogen and nickel co-doped cobalt selenide ultrathin nanosheet. The method does not need to use noble metal, reduces the cost, and has simple preparation process and easy implementation. Experimental results show that when the nitrogen and nickel co-doped cobalt selenide ultrathin nanosheet obtained by the preparation method is used for producing hydrogen by electrolyzing water in 1M KOH solution, the current density is 10 mA-cm‑2And in the process, the overvoltage is 220mV, which is obviously lower than cobalt selenide, nitrogen-doped cobalt selenide and nickel-doped cobalt selenide, and the catalyst has excellent electro-catalytic performance.
Description
Technical Field
The invention relates to the technical field of catalysts for hydrogen production by water electrolysis, in particular to a nitrogen and nickel co-doped cobalt selenide ultrathin nanosheet and a preparation method and application thereof.
Background
Since the 21 st century, the problem of fossil energy has become more and more serious, and as the reserves of fossil fuels are limited, the exhaustion of fossil energy is inevitable as the human beings continuously exploit and utilize the fossil fuels. In view of the above, the search for a new clean, renewable energy source is the direction of energy development in the future. Because water resources on earth are quite abundant, people pay more attention to the research of the hydrolysis field, and energy in the form of light or electricity can be converted into chemical energy to be stored by decomposing water into hydrogen and oxygen. The electrochemical decomposition water is clean, environment-friendly and pollution-free because no other byproducts are generated in the whole process, so that the hydrogen production by electrolyzing water is greatly concerned and has been researched in a large quantity. The hydrogen production by water electrolysis needs to use catalysts, namely a hydrogen evolution reaction catalyst of a cathode and an oxygen evolution reaction catalyst of an anode, the catalyst with the best performance and the most extensive application is a noble metal catalyst such as platinum (Pt), iridium (Ir), ruthenium (Ru) and the like, but the catalyst is expensive and deficient in resources, so that the search for a high-efficiency, stable and cheap alternative electrocatalytic material for large-scale water electrolysis system is very important.
Transition Metal Chalcogenides (TMCs) are getting more and more attention from researchers because of their low cost and abundant resources, and their relatively good HER performance. Cobalt selenide, as a typical TMC material, is considered as an abundant, cheap and efficient hydrogen evolution electrocatalyst because of its excellent metal properties, which can promote the rapid transport of charges on the surfaces of electrodes and catalysts. At present, a plurality of researchers do relevant research on the preparation and the electrocatalytic performance of cobalt selenide, and the research mainly focuses on the doping of the cobalt selenide. For example, Tao Meng et al (In situ coupling of Co 0.85 Se and N-bonded carbon via one-step selection of metallic-organic structures as a three functional catalyst for over water separation and Zn-air batteries [ J ], Meng T, Qin J, Wang S, et al, Journal of Materials Chemistry A,2017,5(15)) prepared composite cobalt selenide nanocrystals and N-doped carbon, improved cobalt selenide electrocatalytic activity to some extent, but the process is complicated and not suitable for industrial production and application; zhao X et al (Engineering the Electrical Conductivity of Lamellar Silver-dopedcobalt (ii) Selenide Nanobelts for Enhanced Oxygen Evolution [ J ], Zhao X, Zhang H, Yan Y, et al, angelwald Chemie,2017,56(1)) use two-dimensional layered cobalt Selenide Nanobelts as a basis, and introduce a trace amount of Silver ions by an ion exchange method to obtain a Silver ion doped cobalt Selenide nanocatalyst, which can also improve the electrocatalytic activity of cobalt Selenide, but the method is doped with metallic Silver, and has expensive price and higher cost, and is not suitable for industrial production and application.
Disclosure of Invention
The invention aims to provide a nitrogen and nickel codoped cobalt selenide ultrathin nanosheet and a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a nitrogen and nickel codoped cobalt selenide ultrathin nanosheet, which comprises the following steps:
(1) mixing a cobalt source, a selenium source, a nickel source, a nitrogen source, water and diethylenetriamine, and carrying out a solvothermal reaction to obtain a nitrogen and nickel co-doped cobalt selenide precursor;
(2) and washing and drying the nitrogen and nickel co-doped cobalt selenide precursor to obtain the nitrogen and nickel co-doped cobalt selenide ultrathin nanosheet.
Preferably, the solvothermal reaction is carried out under closed conditions; the temperature of the solvothermal reaction is 160-220 ℃, and the time is 12-24 h.
Preferably, the molar ratio of the cobalt source, the selenium source, the nickel source and the nitrogen source is 0.8-0.9: 1: 0.1-0.2: 1-3 in terms of cobalt atoms, selenium atoms, nickel atoms and nitrogen atoms.
Preferably, the volume ratio of the selenium atom in the selenium source to the volume of water and the volume of diethylenetriamine is 1mol: 10-15 mL: 20-30 mL.
Preferably, the washing comprises an alcohol washing and a water washing performed in this order.
Preferably, the nickel source is at least one of nickel nitrate, nickel chloride and nickel acetate.
Preferably, the nitrogen source is at least one of dicyandiamide and urea.
Preferably, the selenium source is sodium selenite; the cobalt source is cobalt acetate tetrahydrate.
The invention also provides the nitrogen and nickel co-doped cobalt selenide ultrathin nanosheet obtained by the preparation method in the technical scheme, wherein the thickness of the lamella of the nitrogen and nickel co-doped cobalt selenide ultrathin nanosheet is less than 10 nm.
The invention also provides the application of the nitrogen and nickel codoped cobalt selenide ultrathin nanosheet obtained by the preparation method in the technical scheme or the nitrogen and nickel codoped cobalt selenide ultrathin nanosheet in the technical scheme as a catalyst for hydrogen production by electrolyzing water.
The invention provides a preparation method of a nitrogen and nickel codoped cobalt selenide ultrathin nanosheet, which comprises the following steps: (1) mixing a cobalt source, a selenium source, a nickel source, a nitrogen source, water and diethylenetriamine, and carrying out a solvothermal reaction to obtain a nitrogen and nickel co-doped cobalt selenide precursor; (2) and washing and drying the nitrogen and nickel co-doped cobalt selenide precursor to obtain the nitrogen and nickel co-doped cobalt selenide ultrathin nanosheet. According to the invention, a nitrogen and nickel codoped cobalt selenide precursor is obtained through a solvothermal reaction, in the solvothermal reaction process, a cobalt source and a selenium source react to generate cobalt selenide, nickel atoms in the nickel source replace part of cobalt atoms in the cobalt selenide, nitrogen atoms in a nitrogen source replace part of selenium atoms in the cobalt selenide, and amino groups in diethylenetriamine guide metal cobalt selenide to be arranged into a lamellar structure; according to the invention, the nitrogen and nickel co-doped cobalt selenide precursor is washed to remove anionic impurities and diethylenetriamine in the precursor, and then the precursor is dried to obtain the nitrogen and nickel co-doped cobalt selenide ultrathin nanosheet. The method does not need to use noble metal, reduces the cost, and has simple preparation process and easy implementation. Experimental results show that when the nitrogen and nickel co-doped cobalt selenide ultrathin nanosheet obtained by the preparation method is used for preparing hydrogen by electrolyzing water in a 1M KOH solution, the current density is 10 mA-cm-2And in the process, the overvoltage is 220mV, which is obviously lower than cobalt selenide, nitrogen-doped cobalt selenide and nickel-doped cobalt selenide, and the catalyst has excellent electro-catalytic performance.
Drawings
FIG. 1 is an XRD (X-ray diffraction) pattern of the nitrogen and nickel co-doped cobalt selenide ultrathin nanosheet obtained in example 1;
FIG. 2 is an SEM image and a TEM image of the nitrogen and nickel co-doped cobalt selenide ultrathin nanosheet obtained in example 1;
FIG. 3 is an SEM image and a TEM image of the nitrogen and nickel co-doped cobalt selenide ultrathin nanosheet obtained in example 2;
FIG. 4 is an XPS diagram of the nitrogen and nickel co-doped cobalt selenide ultrathin nanosheets obtained in example 2;
FIG. 5 is an SEM image and a TEM image of the nitrogen and nickel codoped cobalt selenide ultrathin nanosheets obtained in example 3;
FIG. 6 is an SEM image and a TEM image of the nitrogen and nickel codoped cobalt selenide ultrathin nanosheets obtained in example 4;
FIG. 7 is an SEM image and a TEM image of the nitrogen and nickel codoped cobalt selenide ultrathin nanosheets obtained in example 5;
FIG. 8 is a graph of the AC impedance of the products obtained in example 5 and comparative example 1;
FIG. 9 shows polarization curves of the products obtained in example 5 and comparative examples 1 to 3 for hydrogen production by water electrolysis in 1M KOH solution;
FIG. 10 is a graph for testing the cycling stability of the nitrogen and nickel co-doped cobalt selenide ultrathin nanosheets obtained in example 5;
FIG. 11 is a cyclic voltammetry curve of the products obtained in example 5 and comparative examples 1 to 3 for hydrogen production by water electrolysis in a 1M KOH solution;
FIG. 12 is a graph showing the relationship between the capacitance current and the sweep rate in the case of electrolyzing water in a 1M KOH solution to produce hydrogen from the products obtained in example 5 and comparative examples 1 to 3.
Detailed Description
The invention provides a preparation method of a nitrogen and nickel codoped cobalt selenide ultrathin nanosheet, which comprises the following steps:
(1) mixing a cobalt source, a selenium source, a nickel source, a nitrogen source, water and diethylenetriamine, and carrying out a solvothermal reaction to obtain a nitrogen and nickel co-doped cobalt selenide precursor;
(2) and washing and drying the nitrogen and nickel co-doped cobalt selenide precursor to obtain the nitrogen and nickel co-doped cobalt selenide ultrathin nanosheet.
According to the invention, a cobalt source, a selenium source, a nickel source, a nitrogen source, water and diethylenetriamine are mixed for solvothermal reaction to obtain a nitrogen and nickel co-doped cobalt selenide precursor. In the invention, in the process of solvothermal reaction, a cobalt source and a selenium source react to generate cobalt selenide, nickel atoms in the nickel source replace part of cobalt atoms in the cobalt selenide, nitrogen atoms in a nitrogen source replace part of selenium atoms in the cobalt selenide, and amino in diethylenetriamine guides metal cobalt selenide to be arranged into a lamellar structure to play a role of a soft template.
In the present invention, the selenium source is preferably sodium selenite; the cobalt source is preferably cobalt acetate tetrahydrate; the nickel source is preferably at least one of nickel nitrate, nickel chloride and nickel acetate; the nitrogen source is preferably at least one of dicyandiamide and urea.
In the invention, the molar ratio of the cobalt source, the selenium source, the nickel source and the nitrogen source is preferably 0.8-0.9: 1: 0.1-0.2: 1-3 in terms of cobalt atoms, selenium atoms, nickel atoms and nitrogen atoms.
In the invention, the ratio of the amount of the selenium atom in the selenium source to the volume of water and the volume of diethylenetriamine is preferably 1mol: 10-15 mL: 20-30 mL.
The invention has no special limitation on the mixing sequence of the cobalt source, the selenium source, the nickel source, the nitrogen source, the water and the diethylenetriamine, and can obtain the feed liquid which is uniformly mixed. In the embodiment of the invention, preferably, the cobalt source, the selenium source, the nickel source and the nitrogen source are dissolved in water, and then the diethylenetriamine is added to be uniformly mixed; the dissolving mode is preferably stirring-assisted ultrasound, and the mixing mode is preferably stirring.
In the present invention, the solvothermal reaction is preferably carried out under closed conditions; the temperature of the solvothermal reaction is preferably 160-220 ℃, and more preferably 180-220 ℃; the solvothermal reaction time is preferably 12-24 hours, and more preferably 15-20 hours.
After the solvothermal reaction is finished, the feed liquid obtained by the solvothermal reaction is preferably cooled to room temperature, and then solid-liquid separation is carried out to obtain the nitrogen-nickel co-doped cobalt selenide precursor.
The solid-liquid separation method is not particularly limited, and the solid can be separated. In the embodiment of the invention, preferably, the feed liquid obtained by the solvothermal reaction is stood for layering, and then the upper liquid is poured out to obtain a solid, namely the nitrogen and nickel co-doped cobalt selenide precursor.
After the nitrogen and nickel co-doped cobalt selenide precursor is obtained, the nitrogen and nickel co-doped cobalt selenide precursor is washed and dried to obtain the nitrogen and nickel co-doped cobalt selenide ultrathin nanosheet.
In the invention, the washing comprises alcohol washing and water washing which are carried out in sequence; the mode of alcohol washing and water washing is preferably centrifugal washing. In the present invention, the alcohol wash is capable of removing diethylenetriamine; the water wash is capable of removing water-soluble impurities (such as unreacted selenium source, nickel source, and cobalt source).
In the present invention, the washing liquid used for the alcohol washing is preferably absolute ethyl alcohol; the washing liquid used for washing the water is preferably distilled water; the number of times of alcohol washing and water washing is independently 3-8 times.
The dosage of the washing liquid used for alcohol washing and water washing is not specially limited, and the cobalt selenide precursor co-doped with nitrogen and nickel can be immersed.
In the present invention, the drying is preferably vacuum drying; the drying temperature is preferably 60-100 ℃, and more preferably 75-85 ℃; the drying time is preferably 6-24 hours, and more preferably 12-20 hours.
The invention also provides the nitrogen and nickel co-doped cobalt selenide ultrathin nanosheet obtained by the preparation method in the technical scheme, wherein the thickness of the lamella of the nitrogen and nickel co-doped cobalt selenide ultrathin nanosheet is less than 10 nm.
The invention also provides an application of the nitrogen and nickel co-doped cobalt selenide ultrathin nanosheet obtained by the preparation method in the technical scheme or the nitrogen and nickel co-doped cobalt selenide ultrathin nanosheet in the technical scheme as a catalyst for hydrogen production by electrolyzing water.
The specific method of the application is not particularly limited, and the catalyst can be used according to the conventional method for producing hydrogen by electrolyzing water.
The nitrogen-nickel co-doped cobalt selenide ultrathin nanosheet and the preparation method and application thereof provided by the invention are described in detail below with reference to the examples, but the nitrogen-nickel co-doped cobalt selenide ultrathin nanosheet and the preparation method and application thereof cannot be understood as limiting the scope of the invention.
Example 1
Sequentially adding 0.200g of cobalt acetate tetrahydrate, 0.173g of sodium selenite, 0.037g of nickel nitrate and 0.84g of dicyanodiamine into a beaker, adding 10mL of water, performing ultrasonic treatment for 5min, adding 20mL of diethylenetriamine after solid particles are completely dissolved, magnetically stirring for 20min, pouring into a 50mL reaction kettle for sealing, placing the reaction kettle into a crucible furnace, and performing constant-temperature reaction at 160 ℃ for 12 h; after the reaction is finished, naturally cooling the reaction kettle to room temperature, and pouring out the upper-layer liquid to obtain a solid; and (3) centrifuging and washing the solid for 3 times by using absolute ethyl alcohol and distilled water in sequence, and then placing the solid in a vacuum drying oven to be dried for 24 hours at the temperature of 60 ℃ in vacuum to obtain the nitrogen and nickel co-doped cobalt selenide ultrathin nanosheet.
The XRD pattern of the nitrogen and nickel co-doped cobalt selenide ultrathin nanosheet obtained in the example is tested, and the result is shown in FIG. 1. The 2 theta angles in fig. 1 are 33.264 deg., 44.736 deg., 50.562 deg., 60.387 deg., 61.866 deg. and 69.919 deg., respectively corresponding to the Co0.85Characteristic diffraction peaks of (101), (102), (110), (103), (112) and (202) crystal planes of Se, and the spectrum is compared with that of Co0.85The standard card of Se is shifted to the right by a certain angle, which indicates that the catalyst obtained in the example is Ni, N-Co0.85Se (namely nitrogen and nickel codoped cobalt selenide), and due to the doping of Ni and N, the peak corresponding to the doped cobalt selenide is shifted.
The morphology of the nitrogen and nickel co-doped cobalt selenide ultrathin nanosheet obtained in the embodiment is characterized, and the result is shown in fig. 2, wherein a on the left side is an SEM image, and a b on the right side is a TEM image. As can be seen from fig. 2, the product obtained in this embodiment has a nanosheet structure and the nanosheet is very thin, and as a result of measurement, the thickness of the nanosheet layer of the product obtained in this embodiment is less than 10 nm.
The X-ray photon energy spectrum analysis of the nitrogen and nickel co-doped cobalt selenide ultrathin nanosheet obtained in the embodiment is tested, and the result shows that characteristic peaks of nickel, nitrogen, selenium and cobalt exist in the product, so that the successful doping of nickel and nitrogen into cobalt selenide is proved.
Example 2
Sequentially adding 0.224g of cobalt acetate tetrahydrate, 0.173g of sodium selenite, 0.018g of nickel nitrate and 0.168g of dicyanodiamide into a beaker, adding 13mL of water, performing ultrasonic treatment for 5min, adding 26mL of diethylenetriamine after solid particles are completely dissolved, magnetically stirring for 25min, pouring into a 50mL reaction kettle, sealing, placing the reaction kettle into a crucible furnace, and reacting at the constant temperature of 200 ℃ for 18 h; after the reaction is finished, naturally cooling the reaction kettle to room temperature, and pouring out the upper-layer liquid to obtain a solid; and (3) centrifuging and washing the solid for 5 times by using absolute ethyl alcohol and distilled water in sequence, and then placing the solid in a vacuum drying oven to be dried for 12 hours in vacuum at the temperature of 80 ℃ to obtain the nitrogen and nickel codoped cobalt selenide ultrathin nanosheet.
The XRD pattern of the nitrogen and nickel co-doped cobalt selenide ultrathin nanosheet obtained in the embodiment is tested, and the result is consistent with that in figure 1.
The morphology of the nitrogen and nickel co-doped cobalt selenide ultrathin nanosheet obtained in the embodiment is characterized, and the result is shown in fig. 3, wherein the left side a is an SEM image, and the right side b is a TEM image. As can be seen from fig. 3, the product obtained in this embodiment has a nanosheet structure and the nanosheet is very thin, and as a result of measurement, the thickness of the nanosheet layer of the product obtained in this embodiment is less than 10 nm.
The X-ray photon energy spectrum analysis of the nitrogen-nickel co-doped cobalt selenide ultrathin nanosheet obtained in this example was tested, and the result is shown in fig. 4, where a is a nitrogen spectrogram, b is a nickel spectrogram, c is a cobalt spectrogram, and d is a selenium spectrogram. From the nitrogen spectrum in FIG. a, the binding energy of N1s is 399.4 eV; FIG. b shows XPS spectra for Ni2p with binding energies 856.0eV and 873.6eV for Ni2p3/2And Ni2p1/2The valence states of the corresponding Ni elements are Ni2+And Ni3+(ii) a The cobalt spectrum of panel c corresponds to Co2p3/2And Co2p1/2(d) Is the XPS spectrum of Co2p, with diffraction peaks at 780.9eV and 797.2eV corresponding to the signal peaks of Co2p1/2 and 778.5eV and 793.5eV corresponding to Co2p3/2Signal peak of (2), indicating Ni, N-Co0.85The Se catalyst contains bivalent cobalt and trivalent cobalt, which shows that nitrogen and phosphorus are double-doped with cobalt selenide (N, Ni-Co)0.85Se) with Co2+And Co3+Two valence states; FIG. d is a spectrum of selenium, Se3d corresponding to a binding energy of 54.5eV, indicating the presence of Se in the catalyst2-. From the information, characteristic peaks of nickel, nitrogen, selenium and cobalt exist in the product, and the successful doping of nickel and nitrogen into cobalt selenide is proved.
Example 3
Sequentially adding 0.200g of cobalt acetate tetrahydrate, 0.173g of sodium selenite, 0.05g of nickel acetate and 0.180g of urea into a beaker, adding 20mL of water, performing ultrasonic treatment for 10min, adding 30mL of diethylenetriamine after solid particles are completely dissolved, performing magnetic stirring for 30min, pouring into a 50mL reaction kettle, sealing, placing the reaction kettle into a crucible furnace, and performing constant-temperature reaction at 220 ℃ for 24 h; after the reaction is finished, naturally cooling the reaction kettle to room temperature, and pouring out the upper-layer liquid to obtain a solid; and (3) centrifuging and washing the solid for 6 times by using absolute ethyl alcohol and distilled water in sequence, and then placing the solid in a vacuum drying oven to be dried for 6 hours at 70 ℃ in vacuum to obtain the nitrogen and nickel co-doped cobalt selenide ultrathin nanosheet.
The XRD pattern of the nitrogen and nickel co-doped cobalt selenide ultrathin nanosheet obtained in the embodiment is tested, and the result is consistent with that in figure 1.
The morphology of the nitrogen-nickel co-doped cobalt selenide ultrathin nanosheet obtained in the embodiment is characterized, and the result is shown in fig. 5, wherein the left side a is an SEM image, and the right side b is a TEM image, and the thickness of the nanosheet layer of the product obtained in the embodiment is measured to be less than 10 nm.
The X-ray photon energy spectrum analysis of the nitrogen and nickel co-doped cobalt selenide ultrathin nanosheet obtained in the embodiment is tested, the result is consistent with that in fig. 4, the characteristic peaks of nickel, nitrogen, selenium and cobalt exist in the product, and the successful doping of nickel and nitrogen into cobalt selenide is proved.
Example 4
Sequentially adding 0.224g of cobalt acetate tetrahydrate, 0.173g of sodium selenite, 0.02g of nickel nitrate and 0.084g of dicyanodiamide into a beaker, adding 13mL of water, performing ultrasonic treatment for 10min, adding 26mL of diethylenetriamine after solid particles are completely dissolved, magnetically stirring for 30min, pouring into a 50mL reaction kettle, sealing, placing the reaction kettle into a crucible furnace, and performing constant-temperature reaction at 220 ℃ for 16 h; after the reaction is finished, naturally cooling the reaction kettle to room temperature, and pouring out the upper-layer liquid to obtain a solid; and (3) centrifuging and washing the solid for 6 times by using absolute ethyl alcohol and distilled water in sequence, and then placing the solid in a vacuum drying oven to be dried for 12 hours at 70 ℃ in vacuum to obtain the nitrogen and nickel co-doped cobalt selenide ultrathin nanosheet.
The XRD pattern of the nitrogen and nickel co-doped cobalt selenide ultrathin nanosheet obtained in the embodiment is tested, and the result is consistent with that in figure 1.
The morphology of the nitrogen-nickel co-doped cobalt selenide ultrathin nanosheet obtained in the embodiment is characterized, and the result is shown in fig. 6, wherein the left side a is an SEM image, and the right side b is a TEM image, and the thickness of the nanosheet layer of the product obtained in the embodiment is measured to be less than 10 nm.
The X-ray photon energy spectrum analysis of the nitrogen and nickel co-doped cobalt selenide ultrathin nanosheet obtained in the embodiment is tested, the result is consistent with that in fig. 4, the characteristic peaks of nickel, nitrogen, selenium and cobalt exist in the product, and the successful doping of nickel and nitrogen into cobalt selenide is proved.
Example 5
Sequentially adding 0.224g of cobalt acetate tetrahydrate, 0.173g of sodium selenite, 0.026g of nickel chloride and 0.168g of dicyanodiamine into a beaker, adding 13mL of water, performing ultrasonic treatment for 15min, adding 26mL of diethylenetriamine after solid particles are completely dissolved, magnetically stirring for 30min, pouring into a 50mL reaction kettle, sealing, placing the reaction kettle into a crucible furnace, and performing constant-temperature reaction at 220 ℃ for 16 h; after the reaction is finished, naturally cooling the reaction kettle to room temperature, and pouring out the upper-layer liquid to obtain a solid; and (3) centrifuging and washing the solid for 6 times by using absolute ethyl alcohol and distilled water in sequence, and then placing the solid in a vacuum drying oven to be dried for 12 hours at 70 ℃ in vacuum to obtain the nitrogen and nickel co-doped cobalt selenide ultrathin nanosheet.
The XRD pattern of the nitrogen and nickel co-doped cobalt selenide ultrathin nanosheet obtained in the embodiment is tested, and the result is consistent with that in figure 1.
The morphology of the nitrogen-nickel co-doped cobalt selenide ultrathin nanosheet obtained in the embodiment is characterized, and the result is shown in fig. 7, wherein the left side a is an SEM image, and the right side b is a TEM image, and the thickness of the nanosheet layer of the product obtained in the embodiment is measured to be less than 10 nm.
The X-ray photon energy spectrum analysis of the nitrogen and nickel co-doped cobalt selenide ultrathin nanosheet obtained in the embodiment is tested, the result is consistent with that in fig. 4, the characteristic peaks of nickel, nitrogen, selenium and cobalt exist in the product, and the successful doping of nickel and nitrogen into cobalt selenide is proved.
Comparative example 1
Cobalt selenide was prepared according to the preparation method of example 5, without adding nickel chloride and dicyanodiamine.
Comparative example 2
Nickel-doped cobalt selenide was prepared according to the preparation method of example 5, without adding dicyanodiamine.
Comparative example 3
Nitrogen-doped cobalt selenide was prepared according to the preparation method of example 5, without adding nickel chloride.
To implementationThe products of example 5 and comparative example 1 were subjected to impedance testing in a 1M KOH solution, the results are shown in FIG. 8, where Co is0.85Se is cobalt selenide, N, Ni-Co obtained in comparative example 10.85Se is the nitrogen and nickel codoped cobalt selenide ultrathin nanosheet obtained in example 5. The curve is composed of a semicircle of the high-frequency region and a straight line of the low-frequency region, which respectively correspond to the charge transfer and mass transfer processes, and compared with the diameter of the semicircle of the high-frequency region in the figure, the curve is obviously Ni, N-Co0.85Se<Co0.85Se, indicating that the charge transfer resistance after doping is significantly less than that of undoped, proving that doping with nickel and nitrogen does improve the electronic conductivity of cobalt selenide.
The polarization curves of the products obtained in example 5 and comparative examples 1-3 as cathode catalysts for hydrogen production by water electrolysis in 1M KOH solution were examined, and the results are shown in FIG. 9. When the current density is 10mA cm-2Temporal undoped cobalt (Co) selenide0.85Se, the product of comparative example 1), Ni single doped cobalt selenide (Ni-Co)0.85Se, the product of comparative example 2), N mono-doped cobalt selenide (N-Co)0.85Se, the product of comparative example 3) and Ni, N Co-doped cobalt selenide (Ni, N-Co)0.85Se, the product obtained in example 5) has overvoltage of 340mV, 255mV, 260mV and 220mV respectively, and nitrogen and nickel codoped cobalt selenide (Ni, N-Co)0.85Se) is obviously lower than that of other samples, which shows that the electrocatalytic activity of the nitrogen and nickel codoped cobalt selenide is more excellent.
The cyclic stability of the nitrogen and nickel co-doped cobalt selenide ultrathin nanosheet obtained in example 5 is detected, and the result is shown in fig. 10. After 1000 cycles of cyclic voltammetry stability test, the polarization curve of the nitrogen and nickel co-doped cobalt selenide ultrathin nanosheet is not changed obviously, and when the current density is 10 mA-cm-2In the process, the voltage required before and after the cycle test is only increased by 5mV, which shows that the nitrogen and nickel co-doped cobalt selenide ultrathin nanosheet provided by the invention has excellent stability.
The cyclic voltammograms of the products obtained in example 5 and comparative examples 1-3 were measured at different sweep rates in 1M KOH solution (sweep rates of 20, 40, 60, 80, 100, 120, 140, 160mV/s), as shown in FIG. 11, where a is the product obtained in comparative example 1Cyclic voltammogram, b cyclic voltammogram of the product obtained in comparative example 2, c cyclic voltammogram of the product obtained in comparative example 3, and d cyclic voltammogram of the product obtained in example 5. The relationship between the capacitance current and the sweep rate of the products obtained in example 5 and comparative examples 1 to 3 is shown in FIG. 11, in which Co is shown in FIG. 120.85Se is the product obtained in comparative example 1, Ni-Co0.85Se is the product obtained in comparative example 2, N-Co0.85Se is the product obtained in comparative example 3, Ni, N-Co0.85Se is the product obtained in example 5. The current density is linear with the scan rate, and the slope is the electric double layer capacitance, so it can be seen from fig. 12 that example 5 > comparative example 2 > comparative example 3 > comparative example 1. Because the electric double layer capacitance is proportional to the active specific surface area of the electrocatalyst, the results show that the active specific surface area of the nickel-nitrogen co-doped cobalt selenide ultrathin nanosheet is larger than that of undoped cobalt selenide, nickel mono-doped cobalt selenide and nitrogen mono-doped cobalt selenide, so that the active sites can be better utilized, and the enhancement of the electro-catalytic activity is facilitated.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (6)
1. A preparation method of a nitrogen and nickel codoped cobalt selenide ultrathin nanosheet is characterized by comprising the following steps:
(1) mixing a cobalt source, a selenium source, a nickel source, a nitrogen source, water and diethylenetriamine, and carrying out a solvothermal reaction to obtain a nitrogen and nickel co-doped cobalt selenide precursor; the selenium source is sodium selenite; according to the cobalt atom, the selenium atom, the nickel atom and the nitrogen atom, the molar ratio of the cobalt source, the selenium source, the nickel source and the nitrogen source is 0.8-0.9: 1: 0.1-0.2: 1-3; the volume ratio of the selenium atom in the selenium source to the volume of water to the volume of diethylenetriamine is 1mol: 10-15 mL: 20-30 mL; the nitrogen source is at least one of dicyandiamide and urea; the temperature of the solvothermal reaction is 160-220 ℃, and the time is 12-24 hours;
(2) and washing and drying the nitrogen and nickel co-doped cobalt selenide precursor to obtain the nitrogen and nickel co-doped cobalt selenide ultrathin nanosheet.
2. The method of claim 1, wherein the solvothermal reaction is conducted under closed conditions.
3. The method of claim 1, wherein the nickel source is at least one of nickel nitrate, nickel chloride, and nickel acetate.
4. The method of claim 1, wherein the cobalt source is cobalt acetate tetrahydrate.
5. The nitrogen and nickel co-doped cobalt selenide ultrathin nanosheet obtained by the preparation method of any one of claims 1-4, wherein the thickness of the layer of the nitrogen and nickel co-doped cobalt selenide ultrathin nanosheet is less than 10 nm.
6. The nitrogen and nickel co-doped cobalt selenide ultrathin nanosheet obtained by the preparation method according to any one of claims 1 to 4 or the nitrogen and nickel co-doped cobalt selenide ultrathin nanosheet according to claim 5 is used as a catalyst for hydrogen production through electrolysis of water.
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