CN109876846B - Three-dimensional self-supporting Cu3Preparation method of PNW @ CoFeP composite material - Google Patents
Three-dimensional self-supporting Cu3Preparation method of PNW @ CoFeP composite material Download PDFInfo
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Abstract
The invention discloses a three-dimensional self-supporting Cu3The preparation method of the PNW @ CoFeP composite material comprises the following steps: (1) carrying out ultrasonic cleaning on the copper foam by using hydrochloric acid, deionized water and alcohol in sequence; (2) putting the copper foam cleaned in the step (1) into NaOH and sodium thiosulfate for oxidation treatment; (3) cutting the copper hydroxide nanowire array obtained in the step (2) into a working electrode, and performing electrochemical deposition in a mixed solution of ferrous sulfate and cobalt nitrate to obtain a composite material of the copper hydroxide nanowire; (4) and (3) carrying out phosphating treatment on the composite material of the copper hydroxide nanowires and sodium hypophosphite to obtain the composite material. Three-dimensional self-supporting Cu of the invention3The preparation method of the PNW @ CoFeP composite material enables the PNW @ CoFeP composite material to become a potential electrocatalytic full-hydrolytic catalyst through the synergistic effect of metal ion doping and the synergistic effect of active sites between the nanosheets and the nanowires.
Description
Technical Field
The invention belongs to the field of preparation and application of clean sustainable novel energy, and particularly relates to a three-dimensional self-supporting Cu3A preparation method of PNW @ CoFeP composite material.
Background
With the rapid development of economic society, the demand and dependence of energy as a motor for the development of human society are increasing, especially with the intensive consumption of non-renewable fossil energy since the 21 st century, and the serious environmental problems caused by the use of the fossil energy become key factors for the economic development and living environment of all countries around the world. The high heating value, renewable and pollution-free nature of hydrogen has long been considered as a desirable alternative to traditional fossil energy sources. Electrocatalytic decomposition of water in the hydrogen production pathway is considered to be the best hydrogen production route. As a traditional noble metal electrochemical hydrogen and oxygen evolution catalyst, although the catalyst has high-efficiency catalytic activity, the problem of preparation cost thereof seriously limits the large-scale and practical production application of electrocatalytic decomposition water.
The three-dimensional metal foam is a typical catalyst carrier material, and is widely applied to the energy field of batteries, supercapacitors, catalysis and the like due to the unique structure and good rectification effect.
The transition metal phosphide has better physical and chemical properties (higher mechanical strength, conductivity and chemical stability, more coordination unsaturated metal surface atom number), and unique catalytic and electronic properties. The catalyst is used as a non-noble metal compound heterogeneous electrocatalyst for full water splitting, wherein phosphorus and metal sites are respectively used as proton and hydride acceptors, particularly for iron phosphide and cobalt phosphide, the hydrogen adsorption Gibbs free energy is respectively distributed on two sides of an ideal Gibbs free energy value, and the hydrogen adsorption Gibbs free energy of iron cobalt phosphide can be closer to a theoretical optimal value by doping metal atoms. In addition, the designed flaky cobalt iron phosphide can increase the specific surface area of the catalyst and the number of catalytic active sites to improve the catalytic performance.
The stability of the catalyst is improved by introducing the transition metal copper phosphide nanowire due to the excellent conductivity and the synergistic effect of different active sites between the copper phosphide and the cobalt iron phosphide, the specific surface area and the number of the active sites of the catalyst can be obviously increased by designing a unique three-dimensional self-supporting structure, and the catalytic performance of the catalyst is obviously improved.
Aiming at the defects of the prior art, the invention provides a three-dimensional self-supporting Cu3A preparation method of PNW @ CoFeP composite material. And is applied to the field of hydrogen production by electrochemical decomposition. The three-dimensional self-supporting Cu3The PNW @ CoFeP compound has the characteristics of unique structure, high catalytic activity, good stability and the like.
Disclosure of Invention
The invention aims to provide three-dimensional self-supporting Cu aiming at overcoming the defects of the prior art3A preparation method of PNW @ CoFeP composite material.
The invention is realized by the following technical scheme:
three-dimensional self-supporting Cu3The preparation method of the PNW @ CoFeP composite material comprises the following steps:
(1) carrying out ultrasonic cleaning on the copper foam by using hydrochloric acid, deionized water and alcohol in sequence, and drying at room temperature;
(2) putting the copper foam cleaned in the step (1) into NaOH and sodium thiosulfate for oxidation treatment to obtain copper hydroxide nanowires;
(3) cutting the copper hydroxide nanowire array obtained in the step (2) into a working electrode, and performing electrochemical deposition in a mixed solution of ferrous sulfate and cobalt nitrate to obtain a composite material of the copper hydroxide nanowire wrapped by the cobalt-iron layered double-metal hydroxide nanosheets;
(4) respectively putting the composite material of the copper hydroxide nanowires obtained in the step (3) and sodium hypophosphite into a tubular furnace, heating and carrying out phosphating treatment to obtain the three-dimensional self-supporting Cu3PNW @ CoFeP composite.
Preferably, the ultrasonic cleaning time in the step (1) is 15min, and the concentration of hydrochloric acid is 2-3 mol/L.
Preferably, the concentration of NaOH and the concentration of sodium thiosulfate in the step (2) are respectively 2.5mol/L and 0.125mol/L, the total volume of NaOH and sodium thiosulfate is 80ml, and the time of oxidation treatment is 15-30 min.
Preferably, the system for electrochemical deposition in step (3) is a three-electrode system, a calomel electrode is used as a reference electrode, and a platinum sheet is used as a counter electrode.
Preferably, the concentration of the mixed solution of ferrous sulfate and cobalt nitrate in the step (3) is 0.025-0.5 mol/L, the electrodeposition potential is-0.8-1.2V, and the deposition time is 8-10 min.
Preferably, the molar concentration ratio of the ferrous sulfate to the cobalt nitrate in the step (3) is 1: 1.
Preferably, the weight of the sodium hypophosphite in the step (4) is 0.5-1 g.
Preferably, the temperature of the phosphating treatment in the step (4) is 300-350 ℃, and the phosphating time is 1.5-3 h.
The invention has the beneficial effects that: preparing a precursor on copper foam with phosphorized copper nanowires by an electrodeposition method, and then preparing three-dimensional self-supporting Cu by simple phosphorization treatment3The PNW @ CoFeP composite material has the characteristics of simple and convenient preparation method, suitability for large-scale batch production, low preparation cost and the like. Three-dimensional self-supporting Cu of the invention3The PNW @ CoFeP composite material is a potential electrocatalytic full-hydrolytic catalyst through the synergistic effect of metal ion doping and the synergistic effect of active sites between the nanosheets and the nanowires. The invention forms copper hydroxide nano-wires on copper foam through chemical oxidation, then prepares a precursor on the nano-wires by an electrodeposition technology, and finally obtains the composite material through phosphating treatment. The copper foam provides a carrier rectification effect, the copper phosphide enables the activity and the stability of the cobalt-iron phosphide during electrocatalysis to be increased through a synergistic effect and good conductivity between catalytic sites, and the cobalt-iron phosphide enables the catalytic activity to be adjusted through the synergistic effect of cobalt phosphide and iron phosphide and a metal ion doping effect, so that the composite material has a good structural morphology, the full water splitting activity is increased, and the service life is prolonged.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of a precursor copper hydroxide nanowire composite wrapped by a cobalt-iron double hydroxide prepared according to the present invention;
FIG. 2 is a three-dimensional self-supporting Cu prepared in accordance with the present invention3Scanning Electron Microscopy (SEM) of PNW @ CoFeP complex;
FIG. 3 is a three-dimensional self-supporting Cu prepared in accordance with the present invention3X-ray diffraction pattern (XRD) of PNW @ CoFeP complex;
FIG. 4 is a three-dimensional self-supporting Cu prepared in accordance with the present invention3Electrochemical hydrogen evolution Polarization curves (Polarization curves) in 1M potassium hydroxide solution of PNW @ CoFeP complex;
FIG. 5 is a three-dimensional self-supporting Cu prepared in accordance with the present invention3Electrochemical oxygen evolution Polarization curves (Polarization curves) of PNW @ CoFeP complex in 1M potassium hydroxide solution.
Detailed Description
The technical solution of the invention is further illustrated below with reference to examples, which are not to be construed as limiting the technical solution.
Example 1:
three-dimensional self-supporting Cu3The preparation method of the P NW @ CoFeP composite material comprises the following steps of:
step (1): 2X 5cm2The copper foam is sequentially ultrasonically cleaned for 20min by 2M hydrochloric acid, deionized water and alcohol, and dried at room temperature;
step (2): putting the copper foam cleaned in the step (1) into 80ml of 2.5M NaOH and 0.125M sodium thiosulfate for oxidation treatment for 20min, and then obtaining copper hydroxide nanowires (Cu (OH) on the copper foam2NW/CF)；
And (3): cutting the copper hydroxide nanowire array obtained in the step (2) into 1 multiplied by 1.2cm2The size of the composite material is used as a working electrode, electrochemical deposition is carried out in a mixed solution of 0.025M ferrous sulfate and 0.025M cobalt nitrate by adopting a three-electrode system, a calomel electrode is used as a reference electrode, a platinum sheet is used as a counter electrode, the deposition potential is-1V, the deposition time is 9min, the composite material of the copper hydroxide nanowire wrapped by the cobalt-iron layered double-metal hydroxide nanosheet is obtained, then the composite material is washed by deionized water for several times, and then the composite material is dried at room temperature;
and (4): putting the reactant obtained in the step (3) and 0.5g of sodium hypophosphite into two porcelain boats respectively, putting the sodium hypophosphite into a tube furnace, putting the sodium hypophosphite at the upper airflow position of the tube furnace, and carrying out phosphating treatment at the temperature of 300 ℃ to obtain the three-dimensional self-supporting Cu3PNW @ CoFeP composite electrodes.
Wherein, fig. 1 is a Scanning Electron Microscope (SEM) image of the precursor cobalt-iron double hydroxide wrapped copper hydroxide nanowire composite prepared by the present invention. From the figure, the precursor bimetal cobalt iron hydroxide is uniformly wrapped on the copper hydroxide nanowire, and the nanowire is grown into a nanosheet with uniform appearance through nucleation.
FIG. 2 is a process of preparing three-dimensional self-supporting Cu according to the present invention3PNW @ CoFeP composite Scanning Electron Microscopy (SEM). From the figure, it can be seen that cobalt iron phosphide is uniformly coated on the copper phosphide nanowire, and the appearance is kept intact after the phosphating treatment.
FIG. 3 is a three-dimensional self-supporting Cu prepared in accordance with the present invention3X-ray diffraction pattern (XRD) of PNW @ CoFeP complex, corresponding to the three strong peaks (Cu) and copper phosphide (Cu) of copper foam, respectively3P), diffraction peak position of cobalt iron phosphide and cobalt phosphide (CoP)2) There was a slight shift in the corresponding diffraction peaks and no iron phosphide (FeP) appeared2) Based on this we conclude that iron atoms are embedded in the cobalt phosphide lattice replacing some of the cobalt atoms, thereby optimizing the overall electronic structure, demonstrating the synthesis of the composite material.
Example 2:
this example uses the three-dimensional self-supporting Cu prepared in example 13The PNW @ CoFeP composite material is used as a self-supporting hydrogen and oxygen evolution electrode.
The method specifically comprises the following steps: three-dimensionally self-supporting Cu to be produced3Cutting the PNW @ CoFeP composite material into 1 multiplied by 0.5cm2The electrode used for hydrogen evolution and oxygen evolution Working Electrode (WE), a saturated calomel electrode as a Reference Electrode (RE) and a platinum wire as a Counter Electrode (CE) form a three-electrode system, and 1M potassium hydroxide is used as electrolyte. And the electrodes were calibrated (SCE + 1.08V).
FIG. 4 is a three-dimensional self-supporting Cu prepared in accordance with the present invention3Electrochemical hydrogen evolution Polarization curves (Polarization curves) of PNW @ CoFeP complex, as seen in FIG. 4, at a current density of 10, 50mA/cm2The overpotential is 100 mV and 175mV respectively, and the electrochemical hydrogen evolution activity is very excellent.
FIG. 5 is a three-dimensional self-supporting Cu prepared in accordance with the present invention3PNW @ CoFeP complex electrochemical oxygen evolution Polarization curves (Polarization curves) which can be seen from the figure at current densities of 10, 50mA/cm2The overpotential is 221 mV and 358mV respectively, and the overpotential also has better oxygen evolution capability. Is provided withIs potential of high-efficiency total hydrolysis catalyst.
The method of the invention prepares three-dimensional self-supporting Cu3The PNW @ CoFeP compound has the advantages of simple and efficient preparation method, easiness for large-scale production and preparation, low preparation cost and excellent hydrogen evolution and oxygen evolution activity.
Claims (5)
1. Three-dimensional self-supporting Cu3The preparation method of the PNW @ CoFeP composite material is characterized by comprising the following steps of:
(1) carrying out ultrasonic cleaning on the copper foam by using hydrochloric acid, deionized water and alcohol in sequence, and drying at room temperature;
(2) putting the copper foam cleaned in the step (1) into NaOH and sodium thiosulfate for oxidation treatment to obtain copper hydroxide nanowires;
(3) cutting the copper hydroxide nanowire array obtained in the step (2) into a working electrode, and performing electrochemical deposition in a mixed solution of ferrous sulfate and cobalt nitrate, wherein the system of the electrochemical deposition is a three-electrode system, a mercury electrode is used as a reference electrode, a platinum sheet is used as a counter electrode, the concentration of the mixed solution of the ferrous sulfate and the cobalt nitrate is 0.025-0.5 mol/L, the molar concentration ratio is 1:1, the electrodeposition potential is-0.8-1.2V, and the deposition time is 8-10 min, so as to obtain the composite material of the copper hydroxide nanowire wrapped by the cobalt-iron layered double metal hydroxide;
(4) respectively putting the composite material of the copper hydroxide nanowires obtained in the step (3) and sodium hypophosphite into a tubular furnace, heating and carrying out phosphating treatment to obtain the three-dimensional self-supporting Cu3PNW @ CoFeP composite.
2. The three-dimensional self-supporting Cu of claim 13The preparation method of the PNW @ CoFeP composite material is characterized in that the ultrasonic cleaning time in the step (1) is 15min, and the hydrochloric acid concentration is 2-3 mol/L.
3. The three-dimensional self-supporting Cu of claim 13The preparation method of the PNW @ CoFeP composite material is characterized in that NaOH and thiosulfide are used in the step (2)The concentration of the sodium is 2.5mol/L and 0.125mol/L respectively, the total volume of NaOH and sodium thiosulfate is 80ml, and the time of oxidation treatment is 15-30 min.
4. The three-dimensional self-supporting Cu of claim 13The preparation method of the PNW @ CoFeP composite material is characterized in that the weight of the sodium hypophosphite in the step (4) is 0.5-1 g.
5. The three-dimensional self-supporting Cu of claim 13The preparation method of the PNW @ CoFeP composite material is characterized in that the temperature of phosphating in the step (4) is 300-350 ℃, and the phosphating time is 1.5-3 hours.
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| CN112391647A (en) * | 2020-10-30 | 2021-02-23 | 陕西科技大学 | Ferrochrome co-doped nickel-based hydroxide self-supporting electrode for full water decomposition and preparation method thereof |
| CN112981442A (en) * | 2021-02-08 | 2021-06-18 | 东南大学 | FeCoMoPC amorphous alloy for alkaline full-hydrolysis and preparation method thereof |
| CN114318408B (en) * | 2021-12-07 | 2023-06-09 | 闽都创新实验室 | Self-supporting Cu 3 P-based heterojunction electrocatalyst and preparation method and application thereof |
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| CN105513831A (en) * | 2015-11-23 | 2016-04-20 | 北京化工大学 | Electrode material in hollow tubular structure, and preparation method for electrode material |
| CN108505058A (en) * | 2018-04-26 | 2018-09-07 | 中国石油大学(华东) | A kind of bimetallic codope composite material for improving complete solution water catalytic activity |
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| CN105513831A (en) * | 2015-11-23 | 2016-04-20 | 北京化工大学 | Electrode material in hollow tubular structure, and preparation method for electrode material |
| CN108505058A (en) * | 2018-04-26 | 2018-09-07 | 中国石油大学(华东) | A kind of bimetallic codope composite material for improving complete solution water catalytic activity |
| CN109107597A (en) * | 2018-08-31 | 2019-01-01 | 华南农业大学 | A kind of transition metal phosphide/g-C3N4Composite material and preparation method and application |
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