CN112108164A - Carbon-coated two-dimensional transition metal phosphide and preparation method and application thereof - Google Patents
Carbon-coated two-dimensional transition metal phosphide and preparation method and application thereof Download PDFInfo
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- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 56
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 44
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 31
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000001257 hydrogen Substances 0.000 claims abstract description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 29
- 239000000243 solution Substances 0.000 claims description 31
- 239000000843 powder Substances 0.000 claims description 25
- 239000013110 organic ligand Substances 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- -1 transition metal salt Chemical class 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 7
- 239000012266 salt solution Substances 0.000 claims description 7
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
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- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
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- 239000011261 inert gas Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
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- 238000003756 stirring Methods 0.000 claims description 2
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- 238000005406 washing Methods 0.000 claims description 2
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- 239000002135 nanosheet Substances 0.000 abstract description 23
- 239000000463 material Substances 0.000 abstract description 20
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- 239000002243 precursor Substances 0.000 description 15
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- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 4
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- NVIVJPRCKQTWLY-UHFFFAOYSA-N cobalt nickel Chemical compound [Co][Ni][Co] NVIVJPRCKQTWLY-UHFFFAOYSA-N 0.000 description 3
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- 150000001868 cobalt Chemical class 0.000 description 2
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- 229910020630 Co Ni Inorganic materials 0.000 description 1
- 229910002440 Co–Ni Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
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- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
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- 150000002815 nickel Chemical class 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
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Images
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-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- B01J35/61—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- 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
Abstract
The invention provides a carbon-coated two-dimensional transition metal phosphide and a preparation method thereof, and application thereof in the field of electrocatalytic hydrogen evolution; the invention is developed around transition metal base phosphide, firstly, the microscopic morphology of the transition metal base phosphide is shaped into a porous structure consisting of two-dimensional nanosheets by a constant-temperature water bath method at room temperature, and then the carbon-coated two-dimensional transition metal phosphide nanocomposite is prepared by a gas-phase phosphating method; the preparation method of the material has the advantages of simple process, low cost, environmental friendliness and the like; the carbon-coated two-dimensional transition metal phosphide nanocomposite prepared by the method has the advantages of large specific surface area, high electron transmission efficiency, good stability and the like, and has a wide application prospect in the field of electrocatalytic hydrogen evolution.
Description
Technical Field
The invention belongs to the technical field of nano-structure functional materials and electrocatalytic hydrogen evolution, and relates to a carbon composite two-dimensional transition metal phosphide, a preparation method thereof and application thereof in electrocatalytic hydrogen evolution.
Background
In recent years, the problems of energy shortage and environmental pollution caused by over-development and utilization of traditional fossil fuels become more serious, and how to effectively develop new energy which is environment-friendly, low in cost, rich in source and renewable becomes a problem to be solved urgently in the human society. Hydrogen energy has received much attention because of its advantages of abundant reserves, high energy density, greenness and no pollution. Among a plurality of hydrogen production technologies, the water electrolysis hydrogen production technology has the advantages of zero emission, high hydrogen production purity and the like, and plays an extremely important role in the hydrogen energy development process. At present, the noble metal-based catalyst platinum (Pt) is considered as an ideal catalyst for hydrogen production by water electrolysis, but the expensive price restricts the large-scale application of the catalyst in industry. Therefore, many researchers have been working on the development of inexpensive, highly efficient non-noble metal electrocatalytic materials.
The transition metal phosphide is formed by occupying a lattice of metal ions with phosphorus atoms in a manner of filling a radius. The material has attracted much attention because of its excellent physicochemical properties such as metalloid property, magnetism, catalytic property and electrical property. At present, there are many reports on the synthesis methods of transition metal phosphide, such as electrodeposition, hydrothermal method, liquid phase method and gas-solid reaction. These methods all suffer from the following disadvantages: a harsh synthesis device is needed, reaction raw materials are toxic and harmful, harsh reaction conditions (high temperature, high pressure and high vacuum) are adopted, and the process is complex and tedious. More importantly, most of the prepared transition metal phosphide catalysts are three-dimensional structures, active sites exposed on the surfaces are relatively few, and the catalytic activity is not high. Compared with a three-dimensional structure, the two-dimensional sheet structure has better electron transport performance, and has larger specific surface area, so that more reactants can be adsorbed. In addition, the three-dimensional frame structure is easily collapsed under high temperature conditions, and if the three-dimensional frame structure is converted into a two-dimensional structure, the stability thereof at high temperature is significantly improved.
The microstructure surface of the nano composite material is coated with a layer of carbon, so that the stability of the nano composite material can be effectively improved, and the electric conductivity of particles and surface electrons can be enhanced. Therefore, the carbon-coated two-dimensional transition metal nanocomposite obtained by the synthesis method with simple operation has great application prospect.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of a carbon-coated two-dimensional transition metal phosphide nanocomposite. The method comprises the steps of mixing transition metal salts and organic ligands in different proportions, keeping the mixture at a constant temperature for 12-24 hours at room temperature to obtain a precursor with a two-dimensional nanosheet structure, then carrying out gas-phase phosphorization on the precursor to obtain a carbon-coated two-dimensional transition metal phosphide nanocomposite, and applying the carbon-coated two-dimensional transition metal phosphide nanocomposite to the field of electrocatalytic hydrogen evolution.
So far, the carbon-coated two-dimensional transition metal phosphide obtained by the method of constant-temperature water bath-gas phase phosphorization at room temperature is not reported, and the material shows excellent hydrogen evolution catalytic performance and stability in an alkaline system. The method is simple to operate, low in cost and free of harsh preparation process conditions, and the prepared material has the advantages of large specific surface area, high electron transmission efficiency, good conductivity, good stability and the like.
The technical scheme of the invention is as follows:
a carbon-coated two-dimensional transition metal phosphide is prepared by the following method:
(1) dissolving a transition metal salt in an organic solvent to obtain a transition metal salt solution; dissolving an organic ligand in an organic solvent to obtain an organic ligand solution; mixing a transition metal salt solution and an organic ligand solution under the stirring condition, standing at the constant temperature of 25-35 ℃ for 12-24 hours to generate a precipitate, centrifugally washing, and drying in vacuum to obtain solid powder;
the ratio of the amount of metal ions to the amount of organic ligand species in the transition metal salt is 1: 0.5 to 4, preferably 1: 1;
the transition metal salt can be at least one of chloride, nitrate, sulfate and acetate of transition metal elements, and preferably nitrate of the transition metal elements; the transition metal element is one or more of Fe, Co, Ni, Cu, Zn and Mn;
the organic ligand is dimethyl imidazole or terephthalic acid, preferably dimethyl imidazole;
the organic solvent used for dissolving the transition metal salt is methanol, ethanol, acetone or dimethylformamide, preferably methanol; the definition of the organic solvent used for dissolving the organic ligand is the same as that of the organic solvent;
in the transition metal salt solution, the concentration of transition metal ions is 0.1 mmol/mL;
in the organic ligand solution, the concentration of the organic ligand is 0.3 mmol/mL;
(2) putting the solid powder obtained in the step (1) and a phosphorus source into a tube furnace, heating to 300-350 ℃ under the protection of inert gas, and calcining for 2-9 h to obtain a carbon-coated two-dimensional transition metal phosphide (the coated carbon is derived from high-temperature carbonization of an organic ligand);
the mass ratio of the solid powder to the phosphorus source is 1: 5-15, preferably 1: 10;
the phosphorus source is selected from red phosphorus, white phosphorus, sodium hypophosphite or trioctylphosphine, and preferably sodium hypophosphite;
the inert gas is nitrogen, argon or helium, preferably nitrogen;
the heating rate of the calcination is 5 ℃/min.
The carbon-coated two-dimensional transition metal phosphide prepared by the method can be applied to electrocatalytic hydrogen evolution reaction.
According to the invention, a precursor with a two-dimensional nanosheet structure can be obtained by regulating and controlling the proportion of the transition metal salt and the organic ligand by using a constant-temperature water bath method which is simple to operate, and then the carbon-coated two-dimensional transition metal phosphide is prepared by a gas-phase phosphating method so as to optimize the hydrogen evolution catalytic performance of the transition metal-based catalyst.
The technical scheme of the invention has the following beneficial effects:
1. the two-dimensional nanosheet material can be prepared by adopting a thermostatic water bath method in an organic phase and regulating and controlling the proportion of the transition metal salt and the organic ligand, and the method has the advantages of low cost, simple equipment and few reaction steps;
2. by the gas-phase phosphating method, the phosphating process and the carbonization process are combined into a whole on the premise of not damaging the microstructure of the material, the prepared nanosheet is regular in structure, has the advantages of large specific surface area, more active sites, good conductivity and the like, and greatly improves the electro-catalytic hydrogen evolution performance.
Drawings
FIG. 1: SEM images (a) and (b) of the CoP @ C precursor prepared by the method of example 1; (c) and (d) is an SEM image after CoP @ C phosphating;
FIG. 2: XRD pattern of CoP @ C sample prepared by the method of example 1;
FIG. 3: LSV plot (a) of CoP @ C samples prepared by the method of example 1 in potassium hydroxide solution; tafel plot (b); ECSA plot (c) and electrochemical impedance plot (d);
FIG. 4: SEM image (a) of NiP @ C precursor prepared by the method of example 2; (b) SEM image after phosphating NiP @ C; (c) EDS plots for NiP @ C samples;
FIG. 5: co prepared by the method of example 31Ni4SEM image (a) of P @ C precursor; (b) is Co1Ni4SEM picture after P @ C phosphating;
FIG. 6: co prepared by the method of example 31Ni4XRD pattern of P @ C sample;
FIG. 7: co prepared by the method of example 31Ni4Graph of LSV of P @ C sample in potassium hydroxide solution.
Detailed Description
The present invention will be described in further detail with reference to the following examples, but the scope of the present invention is not limited thereto.
Example 1: preparation of carbon-coated cobalt phosphide two-dimensional nanosheet and hydrogen evolution performance thereof
(1) Preparation of carbon-coated cobalt phosphide two-dimensional nanosheet
Weighing 3mmol of cobalt nitrate hexahydrate, dissolving the cobalt nitrate hexahydrate in 30mL of methanol solution, performing ultrasonic dissolution to obtain solution A, weighing 3mmol of dimethylimidazole, dissolving the dimethylimidazole in 10mL of methanol solution, and performing ultrasonic dissolution to obtain solution B. Under the condition of magnetic stirring, the solution A and the solution B are quickly mixed, transferred to a water bath environment with the temperature of 35 ℃ and kept stand for 24 hours at constant temperature. Then taking out the powder, centrifuging the powder by using absolute ethyl alcohol to remove supernatant fluid to leave solid powder, and drying the powder in vacuum to obtain the solid powder containing the cobalt salt. The prepared powder is placed in a small porcelain boat, the outer layer is a large porcelain boat which can wrap the small porcelain boat inside up and down, and 1.0g of sodium hypophosphite is weighed in the middle of the large porcelain boat and the small porcelain boat and placed in the middle of a tube furnace. And (3) heating to 350 ℃ at the speed of 5 ℃/min in the nitrogen atmosphere, and preserving the heat for 2 hours to obtain the carbon-coated cobalt phosphide (CoP @ C) with a two-dimensional nanosheet structure.
Fig. 1(a) and (b) are SEM images of the precursor before vapor phase phosphating, and it can be seen that the microscopic morphology of the precursor is composed of ultrathin two-dimensional nanosheets and has a smooth surface. And FIGS. 1(C) and (d) are SEM images of CoP @ C obtained after gas-phase phosphating, it can be seen that slight shrinkage occurs on the surface of a sample after phosphating, the analysis mainly includes carbonization during the phosphating process, organic ligands are gradually converted into inorganic carbon structures, meanwhile organic components such as bound water on the surface are pyrolyzed into small molecular gas to volatilize, and the formed coated carbon structure is more beneficial to improving the performance of the catalyst.
FIG. 2 is an XRD pattern of CoP @ C. By comparison with the standard XRD pattern of CoP, the diffraction peak of CoP @ C is consistent with the standard card of the orthorhombic CoP, and the corresponding diffraction peaks belong to the diffraction of the crystal face of the orthorhombic CoP (011) (111) (211).
(2) Electrochemical hydrogen evolution performance of carbon-coated cobalt phosphide two-dimensional nanosheet material
In the electrochemical performance test of the invention, a three-electrode system is adopted, 4mg of the prepared catalyst material is weighed and uniformly dispersed in a solvent (800 mu L deionized water, 200 mu L ethanol, 80 mu L5 wt.% Nafion solution), ultrasonic treatment is carried out for half an hour, 5 mu L of the prepared catalyst material is dripped on a 3mm glassy carbon electrode to be used as a working electrode, Pt is a counter electrode, a mercury/mercury oxide (Hg/HgO) electrode is a reference electrode, and an electrolytic liquid system is a 1M KOH solution. The linear voltammetry, tafel, electrochemical comparative area and electrochemical impedance spectroscopy tests were performed on an electrochemical workstation model CHI 760D.
FIG. 3(a) is a LSV curve of CoP @ C electrode material in 1M KOH solution, and it can be seen that at a current density of 10mA cm-2In the process, the overpotential of the CoP @ C electrode is 130mV, and the performance reaches the optimal value, because the ultrathin two-dimensional lamellar structure exposes more (211) crystal planes, compared with the (011) crystal plane, the (211) crystal plane is more beneficial to the electrocatalytic hydrogen evolution reaction. FIG. 3(b) is a Tafel plot of CoP @ C electrode in 1M KOH solution with a Tafel plot slope of 81mF · dec-1And the ultrathin slice layer structure can accelerate the transmission rate of electrons. FIG. 3(C) is an ECSA curve of a CoP @ C electrode in 1M KOH solution, and it can be seen that the specific capacitance of the CoP @ C electrode is 7.03mF · dec-1Indicating that the two-dimensional structure has a larger electrochemically active area. FIG. 3(d) is the electrochemical impedance spectrum of CoP @ C electrodes in 1M KOH solution with different ratios, and it can be seen from the diagram that the impedance of CoP @ C is minimum, which shows that the charge transfer kinetics on the interface of the electrocatalyst and the electrolyte is faster, and finally the catalytic performance is greatly improved.
Example 2: preparation of carbon-coated nickel phosphide two-dimensional nanosheet and hydrogen evolution performance thereof
(1) Preparation of carbon-coated nickel phosphide two-dimensional nanosheet
Weighing 3mmol of nickel sulfate powder, dissolving the powder in 30mL of dimethylformamide solution, performing ultrasonic dissolution to obtain solution A, weighing 3mmol of 1, 4-phthalic acid, dissolving the solution in 10mL of dimethylformamide solution, and performing ultrasonic dissolution to obtain solution B. Under the condition of magnetic stirring, the solution A and the solution B are quickly mixed, transferred to a water bath environment with the temperature of 35 ℃ and kept stand for 24 hours. Then taking out and centrifuging the mixture by using absolute ethyl alcohol to remove supernatant fluid to leave solid powder, and drying the solid powder in vacuum to obtain the nickel-containing salt powder. The prepared nickel salt powder is placed in a small porcelain boat, the outer layer of the small porcelain boat is a large porcelain boat which can wrap the small porcelain boat inside up and down, and 1.0g of sodium hypophosphite is weighed in the middle of the large porcelain boat and the small porcelain boat and placed in the middle of a tube furnace. And (3) heating to 350 ℃ at the speed of 5 ℃/min in the nitrogen atmosphere, and preserving the heat for 2 hours to obtain the carbon-coated nickel phosphide (NiP @ C) with the two-dimensional nanosheet structure.
Fig. 4(a) is an SEM image of the precursor before vapor phase phosphating, and it can be seen that the precursor micro-morphology is composed of ultra-thin two-dimensional nanoplates, which are stacked to form a nanoflower shape. FIG. 4(b) is an SEM image of NiP @ C obtained by phosphating, from which it can be seen that the sample remained in the original morphology after phosphating, and no structural collapse occurred. FIG. 4(C) is an energy dispersive X-ray spectroscopy (EDS) of the sample showing a uniform distribution of the elements C, Ni, P, indicating the presence of the elements Ni, P, C in the NiP @ C sample.
(2) Electrochemical hydrogen evolution performance of carbon-coated nickel phosphide two-dimensional nanosheet material
Catalytic Performance test the catalytic performance test described in (2) of example 1 was conducted.
The hydrogen evolution catalytic performance test result of the carbon-coated nickel phosphide two-dimensional nanosheet material NiP @ C prepared in the embodiment 2 shows that: the material has good electro-catalysis hydrogen evolution performance, and the current density is 10mA cm-2The overpotential was 152 mV.
Example 3: preparation of carbon-coated cobalt nickel phosphide bimetal two-dimensional nanosheet and hydrogen evolution performance thereof
(1) Preparation of carbon-coated cobalt nickel phosphide bimetal two-dimensional nanosheet
0.6mmol of cobalt nitrate hexahydrate and 2.4mmol of nickel nitrate hexahydrate are weighed and dissolved in 30mL of ethanol solution, ultrasonic dissolution is carried out to obtain solution A, 3mmol of dimethyl imidazole is weighed and dissolved in 10mL of ethanol solution, and ultrasonic dissolution is carried out to obtain solution B. Under the condition of magnetic stirring, the solution A and the solution B are quickly mixed, transferred to a water bath environment with the temperature of 35 ℃ and kept stand for 24 hours. Then taking out the powder, centrifuging the powder by using absolute ethyl alcohol to remove supernatant fluid to leave solid powder, and drying the powder in vacuum to obtain the powder containing the nickel-cobalt double metal salt. The prepared nickel-cobalt double-metal salt powder is placed in a small porcelain boat, the outer layer of the small porcelain boat is a large porcelain boat which can wrap the small porcelain boat inside up and down, and 1.0g of trioctylphosphine is weighed and placed in the middle section of a tube furnace. Heating to 350 ℃ at the speed of 5 ℃/min under the nitrogen atmosphere and preserving the heat for 2 hours to obtain the carbon-coated cobalt-nickel phosphide bimetal two-dimensional nanosheet (Co-Ni bi-metal two-dimensional nanosheet)1Ni4P@C)。
Fig. 5(a) is an SEM image of the precursor before vapor phase phosphating, and it can be seen that the precursor has a morphology also composed of ultrathin nanosheets, and the sheets are stacked to form a nanoflower shape.FIG. 5(b) shows the formation of Co after phosphating1Ni4The SEM image of P @ C shows that the sample still keeps the original shape after phosphorization, and the shape structure does not collapse.
FIG. 6 shows Co1Ni4XRD pattern of P @ C material, when molar ratio of metal cobalt to nickel is 1:4 and molar ratio of metal salt to organic ligand is 1:1, comparison with standard card JCPDS-712336 shows that Co is1Ni4The diffraction peak of P @ C is matched with the standard card of orthorhombic CoNiP, which shows that the nanocomposite obtained after gas-phase phosphorization is CoNiP.
(2) Electrochemical hydrogen evolution performance of carbon-coated nickel cobalt phosphide bimetallic two-dimensional nanosheet material
Catalytic Performance test the catalytic performance test described in (2) of example 1 was conducted.
The hydrogen evolution catalytic performance test of the carbon-coated nickel cobalt phosphide bi-metal two-dimensional nanosheet material CoNiP @ C prepared in the embodiment 3 shows that the material has good electrocatalytic hydrogen evolution performance, and the current density is 10 mA-cm-2The overpotential was 175 mV.
In the embodiment, the preparation method is a relatively universal method, different transition metal salts are used as metal sources, the precursor with a two-dimensional nanosheet structure can be obtained by regulating the proportion of the metal salts, the organic ligand and the bimetallic precursor in a constant-temperature water bath for 12-24h, and the carbon-coated two-dimensional transition metal phosphide nanocomposite CoP @ C, NiP @ C and Co is obtained by vapor-phase phosphorization1Ni4P @ C, which all show better hydrogen evolution performance in alkaline solution.
Comparative example
There are reports (Journal of Alloys and Compounds 829(2020)154535) of pressing fresh leaves of Magnolia onto graphite sheets, first calcining at 800 ℃ for 2h under nitrogen atmosphere, cooling the sample, immersing the carbonized film in 2M HCl aqueous solution at 60 ℃ for 12h, finally immersing in 2M KOH and standing at 70 ℃ for 2h to obtain a carbon film, then preparing a cobalt salt solution as electrolyte, obtaining a precursor by electrodeposition, and finally 3Calcining at 00 ℃ for 2h to finally obtain a CoP @ C sample, wherein the material shows certain hydrogen evolution performance and has a current density of 10 mA-cm-2The overpotential was 160 mV.
The preparation method of the transition metal phosphide does not have complicated experimental steps and does not need harsh reaction equipment, and the obtained two-dimensional structure has larger specific surface area and is more beneficial to the improvement of catalytic performance.
Claims (7)
1. A carbon-coated two-dimensional transition metal phosphide is characterized by being prepared by the following method:
(1) dissolving a transition metal salt in an organic solvent to obtain a transition metal salt solution; dissolving an organic ligand in an organic solvent to obtain an organic ligand solution; mixing a transition metal salt solution and an organic ligand solution under the stirring condition, standing at the constant temperature of 25-35 ℃ for 12-24 hours to generate a precipitate, centrifugally washing, and drying in vacuum to obtain solid powder;
the ratio of the amount of metal ions to the amount of organic ligand species in the transition metal salt is 1: 0.5 to 4;
transition metal elements in the transition metal salt are one or more of Fe, Co, Ni, Cu, Zn and Mn;
the organic ligand is dimethyl imidazole or terephthalic acid;
(2) putting the solid powder obtained in the step (1) and a phosphorus source into a tubular furnace, heating to 300-350 ℃ under the protection of inert gas, and calcining for 2-9 h to obtain a carbon-coated two-dimensional transition metal phosphide;
the mass ratio of the solid powder to the phosphorus source is 1: 5-15;
the phosphorus source is selected from red phosphorus, white phosphorus, sodium hypophosphite or trioctylphosphine.
2. The carbon-coated two-dimensional transition metal phosphide of claim 1, wherein in step (1), the ratio of the amounts of metal ions to the amount of organic ligand species in the transition metal salt is 1: 1.
3. the carbon-coated two-dimensional transition metal phosphide of claim 1, wherein in the step (1), the transition metal salt is at least one of chloride, nitrate, sulfate and acetate of a transition metal element.
4. The carbon-coated two-dimensional transition metal phosphide of claim 1, wherein in the step (1), the organic solvent for dissolving the transition metal salt is methanol, ethanol, acetone or dimethylformamide; the definition of the organic solvent used for dissolving the organic ligand is the same.
5. The carbon-coated two-dimensional transition metal phosphide of claim 1, wherein in the step (1), the concentration of transition metal ions in the transition metal salt solution is 0.1 mmol/mL; in the organic ligand solution, the concentration of the organic ligand is 0.3 mmol/mL.
6. The carbon-coated two-dimensional transition metal phosphide as defined in claim 1, wherein in the step (2), the mass ratio of the solid powder to the phosphorus source is 1: 10.
7. use of the carbon-coated two-dimensional transition metal phosphide as defined in claim 1 in electrocatalytic hydrogen evolution reactions.
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