CN112108164B - Carbon-coated two-dimensional transition metal phosphide as well as preparation method and application thereof - Google Patents

Carbon-coated two-dimensional transition metal phosphide as well as preparation method and application thereof Download PDF

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CN112108164B
CN112108164B CN202010732154.5A CN202010732154A CN112108164B CN 112108164 B CN112108164 B CN 112108164B CN 202010732154 A CN202010732154 A CN 202010732154A CN 112108164 B CN112108164 B CN 112108164B
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郑华均
杨萍
时晓伟
舒旭伟
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Zhejiang University of Technology ZJUT
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Abstract

The invention provides a carbon-coated two-dimensional transition metal phosphide, a preparation method thereof and application thereof in the field of electrocatalytic hydrogen evolution; the invention is developed around transition metal phosphide, firstly, the microstructure of the transition metal phosphide is shaped into a porous structure formed by two-dimensional nano sheets by a constant temperature water bath method at room temperature, and then a gas-phase phosphating method is adopted to prepare a carbon-coated two-dimensional transition metal phosphide nanocomposite; 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 relatively wide application prospect in the field of electrocatalytic hydrogen evolution.

Description

Carbon-coated two-dimensional transition metal phosphide as well as preparation method and application thereof
Technical Field
The invention belongs to the technical field of nanostructure 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 excessive development and utilization of traditional fossil fuels are becoming serious, and how to effectively develop new energy sources which are environment-friendly, low in cost, abundant in source and renewable has become a problem to be solved in human society. Hydrogen energy is receiving attention because of its advantages of rich reserves, high energy density, green and pollution-free. Among the hydrogen production technologies, the water electrolysis hydrogen production technology has the advantages of zero emission, high hydrogen production purity and the like, and has extremely important position in the hydrogen energy development process. At present, noble metal-based catalyst platinum (Pt) is considered to be an ideal catalyst for hydrogen production by water electrolysis, but the high price restricts the large-scale application of the catalyst in industry. Accordingly, many researchers have been working on developing inexpensive, efficient non-noble metal electrocatalytic materials.
Transition metal phosphides are formed by the occupation of the lattice of metal ions by phosphorus atoms in a radius-filling manner. The material is widely paid attention to because of excellent physicochemical properties such as metalloid characteristics, magnetism, catalytic performance, electrical performance and the like. At present, many reports on the synthesis method of transition metal phosphide are available, such as electrodeposition method, hydrothermal method, liquid phase method and gas-solid reaction. These methods all suffer from the following disadvantages: a severe synthesis device is needed, the reaction raw materials are toxic and harmful, the severe reaction conditions (high temperature, high pressure and vacuum) are adopted, the process is complex and tedious, and the like. More importantly, most of the transition metal phosphide catalysts obtained by preparation have three-dimensional structures, the active sites exposed on the surface are relatively few, and the catalytic activity is low. Compared with the three-dimensional structure, the two-dimensional sheet structure has better electron transmission performance, larger specific surface area and more reactants. 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 nanocomposite is coated with a layer of carbon, so that the stability of the nanocomposite can be effectively improved, and the conductivity of electrons between particles and on the surface can be enhanced. Therefore, the design of the synthesis method with simple operation to obtain the carbon-coated two-dimensional transition metal nanocomposite has great application prospect.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a preparation method of a carbon-coated two-dimensional transition metal phosphide nanocomposite. The method is that after mixing transition metal salts with different proportions and organic ligands, keeping the constant temperature for 12-24 hours at room temperature, a precursor with a two-dimensional nano-sheet structure can be obtained, and then the carbon-coated two-dimensional transition metal phosphide nanocomposite is obtained through gas-phase phosphating and is applied to the field of electrocatalytic hydrogen evolution.
So far, the method for obtaining the carbon-coated two-dimensional transition metal phosphide by using the constant-temperature water bath-gas phase phosphating at room temperature has not been reported yet, and the material has excellent hydrogen evolution catalytic performance and stability in an alkaline system. The method is simple to operate, low in cost, free of strict 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:
the carbon-coated two-dimensional transition metal phosphide is prepared by the following method:
(1) Dissolving 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 the transition metal salt solution and the organic ligand solution under the stirring condition, standing for 12-24 hours at the constant temperature of 25-35 ℃ to generate precipitate, centrifugally washing, and drying in vacuum to obtain solid powder;
the ratio of the amount of metal ions to the organic ligand species in the transition metal salt is 1:0.5 to 4, preferably 1:1, a step of;
the transition metal salt may be at least one of chloride, nitrate, sulfate, acetate of a transition metal element, preferably nitrate of a transition metal element; the transition metal element is one or more of Fe, co, ni, cu, zn, 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 organic solvent used to dissolve the organic ligand is the same;
in the transition metal salt solution, the concentration of transition metal ions is 0.1mmol/mL;
in the organic ligand solution, the concentration of the organic ligand is 0.3mmol/mL;
(2) Placing 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 carbon-coated two-dimensional transition metal phosphide (coated carbon is obtained from high-temperature carbonization of an organic ligand);
the mass ratio of the solid powder to the phosphorus source is 1:5 to 15, preferably 1:10;
the phosphorus source is selected from red phosphorus, white phosphorus, sodium hypophosphite or trioctyl phosphorus, preferably sodium hypophosphite;
the inert gas is nitrogen, argon or helium, preferably nitrogen;
the temperature rising 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.
The invention can obtain a precursor with a two-dimensional nano-sheet structure by utilizing a constant temperature water bath method with simple operation and regulating and controlling the proportion of transition metal salt and organic ligand, and then preparing the carbon-coated two-dimensional transition metal phosphide 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 nano sheet material can be prepared by adopting a constant-temperature water bath method in an organic phase and regulating and controlling the proportion of transition metal salt and organic ligand, and the method has the advantages of low cost, simple equipment and few reaction steps;
2. the gas-phase phosphating method combines phosphating and carbonizing processes into a whole on the premise of not damaging the microstructure of the material, and the prepared nano sheet has the advantages of regular structure, large specific surface area, more active sites, good conductivity and the like, and greatly improves the electrocatalytic hydrogen evolution performance.
Drawings
Fig. 1: SEM images (a) and (b) of cop@c precursor prepared by the method of example 1; (c) and (d) are SEM images 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 sample 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 of nip@c precursor prepared by the method of example 2 (a); (b) is an SEM image after NiP@C phosphating; (c) EDS plot of NiP@C sample;
fig. 5: example 3 Co prepared by the method 1 Ni 4 SEM image of P@C precursor(a) The method comprises the steps of carrying out a first treatment on the surface of the (b) Is Co 1 Ni 4 P@C SEM images after phosphating;
fig. 6: example 3 Co prepared by the method 1 Ni 4 XRD pattern of P@C sample;
fig. 7: example 3 Co prepared by the method 1 Ni 4 LSV plot 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 nanosheets
3mmol of cobalt nitrate hexahydrate is weighed and dissolved in 30mL of methanol solution, ultrasonic dissolution is carried out to obtain solution A, 3mmol of dimethyl imidazole is weighed and dissolved in 10mL of methanol 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 and transferred to a water bath environment with the temperature of 35 ℃ for standing for 24 hours at constant temperature. And taking out, centrifuging with absolute ethyl alcohol to remove supernatant liquid and leave solid powder, and drying in vacuum to obtain the solid powder containing 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 and placed in the middle section of the tubular furnace in the middle of the large porcelain boat and the small porcelain boat. Under the nitrogen atmosphere, heating to 350 ℃ at a speed of 5 ℃/min and preserving heat for 2 hours to obtain the cobalt phosphide (CoP@C) with the two-dimensional nano sheet structure and coated by carbon.
Fig. 1 (a) and (b) are SEM images of a precursor before gas-phase phosphating, and it can be seen that the micro morphology of the precursor consists of ultrathin two-dimensional nano-sheets, and the surface is smooth. And in fig. 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 the sample after phosphating, and the analysis mainly comprises carbonization during the phosphating process, the organic ligand is gradually converted into an inorganic carbon structure, and meanwhile, organic components such as bound water on the surface are pyrolyzed into micromolecular gas for volatilization, so that the formed coated carbon structure is more beneficial to the improvement of the performance of the catalyst.
FIG. 2 is an XRD pattern for CoP@C. By comparison with the standard XRD pattern of CoP, it can be seen that the diffraction peak of CoP@C coincides with the standard card of orthorhombic CoP, and the corresponding diffraction peaks respectively belong to the diffraction of the crystal planes of orthorhombic CoP (011) (111) (211).
(2) Electrochemical hydrogen evolution performance of carbon-coated cobalt phosphide two-dimensional nano-sheet 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 of deionized water, 200 mu L of ethanol, 80 mu L of 5wt.% Nafion solution) for half an hour, 5 mu L of the catalyst material is dripped on a 3mm glassy carbon electrode to serve as a working electrode, pt is a counter electrode, a mercury/mercury oxide (Hg/HgO) electrode is a reference electrode, and an electrolyte system is 1M KOH solution. The linear voltammogram, tafel curve, electrochemical comparison area and electrochemical impedance spectroscopy tests were all performed on a CHI760D electrochemical workstation.
FIG. 3 (a) is a LSV curve of CoP@C electrode material in 1M KOH solution, as seen at a current density of 10mA cm -2 When the over potential of the cop@c electrode is 130mV, the performance reaches an optimal value, because the ultrathin two-dimensional lamellar structure exposes more (211) crystal planes, and the (211) crystal planes are more beneficial to the electrocatalytic hydrogen evolution reaction than the (011) crystal planes. FIG. 3 (b) is a Tafel curve of the CoP@C electrode in 1M KOH solution with a Tafel curve slope of 81 mF.dec -1 The ultrathin lamellar structure is shown to be capable of accelerating the electron transport rate. FIG. 3 (c) is an ECSA curve of the CoP@C electrode in 1M KOH solution, showing that the specific capacitance of the CoP@C electrode is 7.03 mF.dec -1 It is shown that the two-dimensional structure has a larger electrochemically active area. Fig. 3 (d) shows electrochemical impedance spectra of cop@c electrodes in 1M KOH solution according to different ratios, and it can be seen from the figure that the impedance of cop@c is the smallest, which indicates that the charge transfer kinetics at the interface between the electrocatalyst and the electrolyte is faster, and 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 nanosheets
3mmol of nickel sulfate powder is weighed and dissolved in 30mL of dimethylformamide solution, ultrasonic dissolution is carried out to obtain solution A, 3mmol of 1, 4-phthalic acid is weighed and dissolved in 10mL of dimethylformamide solution, and ultrasonic dissolution is carried out to obtain solution B. Solution a and solution B were rapidly mixed with magnetic stirring, transferred to a 35 ℃ water bath environment, and allowed to stand for 24 hours. And taking out, centrifuging with absolute ethyl alcohol to remove supernatant liquid and leave solid powder, and vacuum drying to obtain nickel salt-containing powder. The prepared nickel salt 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 and placed in the middle section of the tubular furnace in the middle of the large porcelain boat and the small porcelain boat. Heating to 350 ℃ at a speed of 5 ℃/min under nitrogen atmosphere, and preserving heat for 2 hours to obtain the carbon-coated nickel phosphide (NiP@C) with a two-dimensional nano sheet structure.
Fig. 4 (a) is an SEM image of a precursor before gas-phase phosphating, and it can be seen that the precursor microstructure is composed of ultrathin two-dimensional nano-sheets, and the sheets are stacked to form a nano-flower shape. Fig. 4 (b) is an SEM image of nip@c obtained by phosphating, from which it can be seen that the sample still maintains its original morphology after phosphating, without structural collapse. FIG. 4 (C) is an energy dispersive X-ray spectroscopy (EDS) of the sample, showing a uniform distribution of the elements C, ni, and P, indicating the presence of the elements Ni, P, and C in the NiP@C sample.
(2) Electrochemical hydrogen evolution performance of carbon-coated nickel phosphide two-dimensional nanosheet material
Catalytic performance test the same catalytic performance test as described in (2) of example 1.
The test result of the hydrogen evolution catalytic performance of the carbon-coated nickel phosphide two-dimensional nano sheet material NiP@C prepared in the embodiment 2 shows that: the material has good electrocatalytic hydrogen evolution performance, and the current density is 10mA cm -2 The overpotential was 152mV.
Example 3: preparation of carbon-coated cobalt-nickel phosphide bimetallic two-dimensional nanosheet and hydrogen evolution performance thereof
(1) Preparation of carbon-coated cobalt-nickel phosphide bimetallic two-dimensional nanosheets
Weighing 0.6mmol of cobalt nitrate hexahydrate and 2.4mmol of nickel nitrate hexahydrate to be dissolved in 30mL of ethanol solution, performing ultrasonic dissolution to obtain solution A, weighing 3mmol of dimethyl imidazole to be dissolved in 10mL of ethanol solution, performing ultrasonic dissolution to obtainTo solution B. Solution a and solution B were rapidly mixed with magnetic stirring, transferred to a 35 ℃ water bath environment, and allowed to stand for 24 hours. And taking out, centrifuging with absolute ethyl alcohol to remove supernatant liquid and leave solid powder, and vacuum drying to obtain powder containing nickel cobalt bimetallic salt. The prepared nickel cobalt bimetallic salt 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 trioctyl phosphorus is weighed and placed in the middle section of a tubular furnace in the middle of the large porcelain boat and the small porcelain boat. Heating to 350 ℃ at a speed of 5 ℃/min under nitrogen atmosphere, and preserving heat for 2 hours to obtain the carbon-coated cobalt-nickel phosphide bimetallic two-dimensional nanosheets (Co 1 Ni 4 P@C)。
Fig. 5 (a) is an SEM image of the precursor before gas-phase phosphating, and it can be seen that the precursor has morphology and is also composed of ultrathin nanosheets, and the sheets are stacked to form nanoflower. FIG. 5 (b) shows the Co obtained after phosphating 1 Ni 4 P@C, it can be seen from the SEM image of the sample that the sample remained in its original morphology after phosphating and no collapse in morphology structure occurred.
FIG. 6 is Co 1 Ni 4 XRD pattern of P@C material, when the molar ratio of metal cobalt to nickel is 1:4 and the molar ratio of metal salt to organic ligand is 1:1, co is known by comparison with standard card JCPLS-712336 1 Ni 4 P@C is matched with the standard card of orthorhombic CoNiP, which shows that the nanocomposite obtained after gas-phase phosphating is CoNiP.
(2) Electrochemical hydrogen evolution performance of carbon-coated nickel-cobalt phosphide bimetallic two-dimensional nanosheet material
Catalytic performance test the same catalytic performance test as described in (2) of example 1.
The test of the hydrogen evolution catalytic performance of the carbon-coated nickel-cobalt phosphide bimetallic two-dimensional nano sheet material CoNiP@C prepared in example 3 shows that the material has good electrocatalytic hydrogen evolution performance and has the current density of 10mA cm -2 At this time, the overpotential was 175mV.
As can be seen from the above examples, the preparation method of the present invention is a more general method, which uses different transition metal salts as metal sources by controlling the metalThe ratio of salt to organic ligand to bimetallic precursor is controlled in a constant temperature water bath for 12-24h to obtain precursor with two-dimensional nano-sheet structure, and then the precursor is subjected to gas phase phosphating to obtain carbon-coated two-dimensional transition metal phosphide nanocomposite CoP@C, niP@C and Co 1 Ni 4 P@C, which show good hydrogen evolution properties in alkaline solutions.
Comparative example
There are studies reporting (Journal of Alloys and Compounds 829 (2020) 154535) that fresh magnolia leaves are pressed on a graphite flake, firstly calcining for 2 hours at 800 ℃ under nitrogen atmosphere, cooling the sample, then immersing the obtained carbonized film in 2M HCl aqueous solution for 12 hours at 60 ℃, finally immersing in 2M KOH and standing for 2 hours at 70 ℃ to finally obtain a carbon film, then preparing cobalt salt solution as electrolyte, obtaining a precursor by electrodeposition, finally calcining for 2 hours at 300 ℃ to finally obtain a CoP@C sample, wherein the material shows a certain hydrogen evolution property, and the current density is 10mA cm -2 The overpotential was 160mV.
It can be seen that the preparation method of the transition metal phosphide has no complicated experimental steps, does not need harsh reaction equipment, and has a two-dimensional structure, larger specific surface area and better promotion of catalytic performance.

Claims (4)

1. The application of the carbon-coated two-dimensional transition metal phosphide in the electrocatalytic hydrogen evolution reaction is characterized in that the carbon-coated two-dimensional transition metal phosphide is prepared by the following steps:
(1) Dissolving 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 the transition metal salt solution and the organic ligand solution under the stirring condition, standing for 12-24 hours at the constant temperature of 25-35 ℃ to generate precipitate, centrifugally washing, and drying in vacuum to obtain solid powder;
the transition metal salt is cobalt nitrate hexahydrate, the organic ligand is dimethyl imidazole, and the mass ratio of the cobalt nitrate hexahydrate to the dimethyl imidazole is 1:1, a step of;
alternatively, the transition metal salt is nickel sulfate, the organic ligand is 1, 4-phthalic acid, and the ratio of the amount of the nickel sulfate to the amount of the substance of 1, 4-phthalic acid is 1:1, a step of;
or the transition metal salt is cobalt nitrate hexahydrate and nickel nitrate hexahydrate, the organic ligand is dimethyl imidazole, and the mass ratio of the cobalt nitrate hexahydrate, the nickel nitrate hexahydrate and the dimethyl imidazole is 1:4:5, a step of;
(2) Placing 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 carbon-coated two-dimensional transition metal phosphide;
the mass ratio of the solid powder to the phosphorus source is 1:5 to 15;
the phosphorus source is selected from red phosphorus, white phosphorus, sodium hypophosphite or trioctyl phosphorus.
2. The use according to claim 1, wherein in step (1) of the preparation method of the carbon-coated two-dimensional transition metal phosphide, the organic solvent used for dissolving the transition metal salt is methanol, ethanol, acetone or dimethylformamide; the definition of organic solvent used to dissolve the organic ligand is the same.
3. The use according to claim 1, wherein in step (1) of the preparation method of the carbon-coated two-dimensional transition metal phosphide, the concentration of transition metal ions in the transition metal salt solution is 0.1mmol/mL; in the organic ligand solution, the concentration of the organic ligand is 0.3mmol/mL.
4. The method according to claim 1, wherein in the step (2) of the preparation method of the carbon-coated two-dimensional transition metal phosphide, the mass ratio of the solid powder to the phosphorus source is 1:10.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107744822A (en) * 2017-10-17 2018-03-02 中国科学院理化技术研究所 Metal phosphide-porous carbon framework composite material and preparation method and application thereof
CN109663608A (en) * 2018-12-27 2019-04-23 北京印刷学院 A kind of carbon-cobalt molybdenum double-metal phosphide composite material and preparation method
CN110639565A (en) * 2018-06-27 2020-01-03 北京印刷学院 Carbon-bimetal phosphide composite material and preparation method thereof
CN111321394A (en) * 2020-02-28 2020-06-23 盱眙新远光学科技有限公司 Method for preparing nano flaky cobalt phosphide by vapor deposition

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9802821B2 (en) * 2015-07-13 2017-10-31 Agency For Science, Technology And Research Method for preparing transition metal phosphide

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107744822A (en) * 2017-10-17 2018-03-02 中国科学院理化技术研究所 Metal phosphide-porous carbon framework composite material and preparation method and application thereof
CN110639565A (en) * 2018-06-27 2020-01-03 北京印刷学院 Carbon-bimetal phosphide composite material and preparation method thereof
CN109663608A (en) * 2018-12-27 2019-04-23 北京印刷学院 A kind of carbon-cobalt molybdenum double-metal phosphide composite material and preparation method
CN111321394A (en) * 2020-02-28 2020-06-23 盱眙新远光学科技有限公司 Method for preparing nano flaky cobalt phosphide by vapor deposition

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