CN110639565A - Carbon-bimetal phosphide composite material and preparation method thereof - Google Patents
Carbon-bimetal phosphide composite material and preparation method thereof Download PDFInfo
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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—
-
- 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
-
- 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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
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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
Abstract
Carbon-bimetal phosphide composite material Ni2P-CoP-C, the composite material is composed of a carbon skeleton having a dodecahedral structure and Ni2Bimetallic phosphide nanoparticles of P-CoP. Ni is prepared on a carbon skeleton matrix with a dodecahedron structure2P-CoP-C composite material, effective maintenance of dodecahedral structure carbon skeleton, ensuring Ni2The P-CoP active substance particles are uniformly dispersed in the porous carbon matrix, so that the aggregation of the P-CoP active substance particles in the reaction process is prevented, and the effective exposure of active sites of a Hydrogen Evolution Reaction (HER) is promoted, thereby improving the catalytic activity of the material; the carbon skeleton can effectively improve the conductivity of the whole catalyst material, thereby further improving the catalytic performance of the catalyst material;the synergistic effect of the phases of the bimetallic phosphide plays an important role in improving the electrochemical catalytic performance.
Description
Technical Field
The invention relates to a carbon-bimetal phosphide composite material Ni2P-CoP-C, a preparation method thereof and application of the composite material in the technical field of electrocatalytic hydrogen production.
Background
The catalytic hydrogen production has the advantages of high efficiency, low energy consumption, environmental friendliness and the like, and is a hydrogen production technology with great application prospect. But because of the serious cathode polarization problem, the energy consumption of the catalytic hydrogen production technology is greatly increased, thereby increasing the hydrogen production cost. Noble metals such as Pt and their alloys have the best electrocatalytic hydrogen evolution properties, but they are expensive and difficult to apply on a large scale. The development of a non-noble metal catalyst with high performance and low cost has important significance for promoting the application of the electrocatalytic hydrogen production technology.
Transition metal (Fe, Co, Ni, Mn) phosphide has the advantages of low cost, excellent hydrogen evolution catalytic activity, various preparation modes and the like, and is rapidly developed in recent years. The bimetallic phosphide has better performance than single metal phosphide due to the synergistic effect of different elements, so that the bimetallic phosphide becomes an ideal material for replacing noble metal electrocatalyst. Junhua Song et al (binary Cobalt-Based phosphor Zeolite intermetallic Framework: CoPx Phase-Dependent electric Conductivity and Hydrogen Atom Adsorption Energy for efficient organic Water dispersing [ J ]. adv. Energy matrix, 2017, 7, 1601555) synthesized Cobalt-Based Bimetallic Phosphide, and the introduction of the second metal element is favorable for enhancing the activity of the transition metal Phosphide.
Disclosure of Invention
The invention aims to provide carbon-bimetal phosphide composite material carbon compounded bimetal phosphide Ni2P-CoP-C, the composite material is composed of a carbon skeleton having a dodecahedral structure and Ni2Bimetallic phosphide nanoparticles of P-CoP.
The shape, size and composition of the bimetallic phosphide double-core material are suitable for electrocatalysisThe activation has obvious influence, and the Ni is prepared and obtained on the carbon skeleton matrix with the dodecahedron structure2P-CoP-C composite material, effective maintenance of dodecahedral structure carbon skeleton, ensuring Ni2The P-CoP active substance particles are uniformly dispersed in the porous carbon matrix, so that the aggregation of the P-CoP active substance particles in the reaction process is prevented, and the effective exposure of active sites of a Hydrogen Evolution Reaction (HER) is promoted, thereby improving the catalytic activity of the material; (2) the carbon skeleton can effectively improve the conductivity of the whole catalyst material, thereby further improving the catalytic performance of the catalyst material; (3) the synergistic effect of the phases of the bimetallic phosphide plays an important role in improving the electrochemical catalytic performance.
The preparation method of the bimetal phosphide composite material comprises the following steps:
1) weighing Co (NO) according to the mass ratio of 1: 1-33)2·6H2O and 2-methylimidazole, dissolving in 100ml methanol, stirring for dissolving, and adding Co (NO) into the 2-methylimidazole solution3)2Stirring the solution, aging the solution at room temperature for 24 hours after stopping stirring, and then centrifugally separating, cleaning and drying the product to obtain the cobalt-based metal organic framework compound with a dodecahedron structure.
2) Placing the cobalt-based metal organic framework compound obtained in the step 1) into a quartz boat, placing the quartz boat into a tubular resistance furnace, heating to 550-900 ℃ in an argon atmosphere, and preserving heat for 1-8 hours to obtain the dodecahedral porous carbon composite material Co-C containing the cobalt metal simple substance.
3) Adding the Co-C composite material obtained in the step 2) into NaOH solution for stirring, and adding 3ml of Ni (NO) in the stirring process3)2The solution was added dropwise and stirred well. Pouring the uniformly stirred solution into a reaction kettle, heating to 100 ℃, preserving heat for 10-30h, and cooling to room temperature to obtain Ni (OH)2-Co-C powder, which is washed and dried;
4) reacting Ni (OH)2the-Co-C powder and the sodium hypophosphite are respectively arranged at two ends of the magnetic boat according to the mass ratio of 1: 5, the magnetic boat is arranged in a tube furnace, the temperature is raised to 200-400 ℃ in the argon atmosphere, the temperature is kept for 0.5-4h for phosphorization, and the temperature is cooled to the room temperatureObtaining the carbon-bimetal phosphide composite material Ni2P-CoP-C。
The cleaning and drying in the step 1) are carried out by washing for 3 times by using methanol and then vacuum drying for 8h at the temperature of 60 ℃.
In the step 2), the temperature is raised to 600 ℃ at the temperature raising rate of 5 ℃/min, and the temperature is kept for 2 h.
The concentration of the NaOH solution in the step 4) is 8mol/L, and the Ni (NO) is3)2The concentration of the solution was 0.05 mol/L.
The method of the invention has the following characteristics:
(1) the cobalt-based metal organic framework compound with a dodecahedron structure is carbonized to obtain the dodecahedron porous carbon matrix material containing a cobalt simple substance, and the phosphorized Ni is ensured2The P-CoP active material particles are uniformly dispersed in the porous carbon matrix.
(2) Co metal in carbon matrix and hydrothermal environment promote Ni (OH)2Nucleation is carried out in the porous carbon, and micron pores in the porous carbon inhibit the growth of the porous carbon, so that particle agglomeration is prevented, and the purpose of improving the specific surface area and enhancing the catalytic activity is achieved.
Drawings
FIG. 1 is an SEM topography of a cobalt-based metal organic framework compound having a dodecahedron structure of step 1) of example 1.
FIG. 2 is the XRD pattern of the dodecahedral porous carbon composite Co-C containing cobalt metal simple substance obtained in step 2) of example 1
FIG. 3 is an SEM image of the dodecahedral porous carbon composite Co-C containing the cobalt metal simple substance obtained in step 2) of example 1.
FIG. 4 shows Ni obtained in example 12XRD pattern of P-CoP-C bimetallic phosphide.
FIG. 5 shows Ni obtained in example 12TEM spectrum of P-CoP-C bimetal phosphide.
FIG. 6 shows Ni obtained in example 12P-CoP-C and comparative examples Co-C, CoP-C, Ni2LSV patterns of electrolyzed water hydrogen evolution for P-C and commercial Pt-C catalysts.
FIG. 7 shows Ni obtained in example 12P-CoP-C and comparative examples Co-C, CoP-C, Ni2P-Tafel spectra of electrolyzed water hydrogen evolution for C and commercial Pt-C catalysts.
Detailed Description
Example 1
1) Weigh 0.498g Co (NO)3)2·6H2O and 0.656g 2-methylimidazole respectively dissolved in 50ml methanol, stirred for 10 minutes, and after the solution is stirred and dissolved, the 2-methylimidazole solution is poured into Co (NO) rapidly3)2And (3) continuing stirring for 10min in the solution, aging for 24h at room temperature after stopping stirring, then centrifugally separating the product, washing for 3 times by using methanol, and finally drying for 8h in vacuum at 60 ℃ to obtain the cobalt-based metal organic framework compound with the dodecahedron structure.
2) Placing the cobalt-based metal organic framework compound with the dodecahedron structure into a quartz boat, placing the quartz boat into a tubular resistance furnace, raising the temperature from the room to the target temperature of 600 ℃ at the temperature rise rate of 5 ℃/min in the argon atmosphere, and keeping the temperature constant for 2 hours to prepare the dodecahedron porous carbon composite material Co-C containing the cobalt metal simple substance.
3) Putting 30mg of the prepared composite Co-C in 10ml of deionized water, performing ultrasonic treatment until the Co-C is uniform and has NO precipitate, adding the Co-C into 20ml of NaOH solution with the concentration of 8mol/L, stirring for 1 hour, and adding 3ml of Ni (NO) with the concentration of 0.05mol/L in the stirring process3)2The solution was added dropwise and stirred well. Pouring the uniformly stirred solution into a 50mL inner lining of a reaction kettle, sealing and screwing the inner lining by using a steel shell, heating to 100 ℃, preserving heat for 24 hours, cooling to room temperature, washing and drying by using ethanol and deionized water, and drying collected particles for 24 hours in vacuum at 60 ℃ to obtain Ni (OH)2-Co-C powder.
4) The obtained Ni (OH)2Placing the-Co-C powder and sodium hypophosphite at the mass ratio of 1: 5 at two ends of a magnetic boat, placing the magnetic boat in a tubular furnace, heating the magnetic boat from room temperature to the target temperature of 300 ℃ at the heating rate of 3 ℃/min in the argon atmosphere, carrying out phosphating at constant speed for 2h, and cooling to room temperature to obtain the carbon-bimetal phosphide composite material Ni2P-CoP-C。
Example 2
1) Synthesis of cobalt-based metal organic framework compounds with dodecahedral structure: weighing 1gCo (NO)3)2·6H2O and 3g of 2-methylimidazole respectively dissolved in 800ml of methanol, stirred for 10 minutes, and after the 2-methylimidazole solution is dissolved by stirring, the 2-methylimidazole solution is poured into Co (NO) rapidly3)2And (3) continuing stirring for 10min in the solution, aging for 12h at room temperature after stopping stirring, then centrifugally separating the product, washing for 3 times by using methanol, and finally drying for 12h in vacuum at 60 ℃ to obtain the cobalt-based metal organic framework compound with the dodecahedron structure.
2) Placing the cobalt-based metal organic framework compound with the dodecahedron structure into a quartz boat, placing the quartz boat into a tubular resistance furnace, heating the quartz boat to a target temperature of 800 ℃ from room temperature at a heating rate of 5 ℃/min in an argon atmosphere, and keeping the temperature constant for 4 hours to prepare the dodecahedron porous carbon composite material Co-C containing the cobalt metal simple substance.
3) Putting the prepared 40mg of composite Co-C in 10ml of deionized water, performing ultrasonic treatment until the composite Co-C is uniform and has NO precipitate, adding the composite Co-C into 30ml of NaOH solution with the concentration of 8mol/L, stirring for 1 hour, and adding 4ml of Ni (NO) with the concentration of 0.08mol/L in the stirring process3)2The solution was added dropwise and stirred well. Pouring the uniformly stirred solution into a 50mL inner lining of a reaction kettle, sealing and screwing the inner lining with a steel shell, heating to 80 ℃, preserving heat for 12h, cooling to room temperature, washing and drying with ethanol and deionized water, and vacuum drying collected particles for 24h at 60 ℃ to obtain Ni (OH)2-Co-C powder.
4) The obtained Ni (OH)2Placing the-Co-C powder and sodium hypophosphite at the mass ratio of 1: 4 at two ends of a magnetic boat, placing the magnetic boat in a tubular furnace, heating the magnetic boat from room temperature to the target temperature of 350 ℃ at the heating rate of 5 ℃/min in the argon atmosphere, carrying out phosphating at constant speed for 3h, and cooling to room temperature to obtain the carbon-bimetal phosphide composite material Ni2P-CoP-C。
Comparative example 1
The dodecahedral porous carbon composite Co-C containing the cobalt metal simple substance obtained in the step 2) of the example 1 is used as an electrocatalytic contrast material.
Comparative example 2
Carrying out phosphating treatment on the dodecahedral porous carbon composite Co-C containing the cobalt metal simple substance obtained in the step 2) in the embodiment 1, respectively placing the Co-C composite and sodium hypophosphite at two ends of a magnetic boat according to the mass ratio of 1: 5, placing the magnetic boat in a tubular furnace, heating to 300 ℃ in argon atmosphere, preserving heat for 2 hours for phosphating, and cooling to room temperature to obtain the carbon-metal phosphide composite CoP-C.
Comparative example 3
Placing the dodecahedral porous carbon composite material Co-C containing the cobalt metal simple substance obtained in the step 2) of the embodiment 1 in an HF aqueous solution, stirring for 24 hours to remove Co, cleaning and collecting with deionized water, and then drying for 24 hours at 60 ℃ under vacuum to obtain porous carbon C-HF treated with HF acid.
Putting the prepared 30mg porous carbon C-HF into 10ml deionized water, performing ultrasonic treatment until the porous carbon C-HF is uniform and has NO precipitate, adding the porous carbon C-HF into 20ml NaOH solution with the concentration of 8mol/L, stirring for 1h, and adding 3ml Ni (NO) with the concentration of 0.05mol/L in the stirring process3)2The solution was added dropwise and stirred well. Pouring the uniformly stirred solution into a 50mL inner lining of a reaction kettle, sealing and screwing the inner lining by using a steel shell, heating to 100 ℃, preserving heat for 24 hours, cooling to room temperature, washing and drying by using ethanol and deionized water, collecting particles, and drying in vacuum for 24 hours at 60 ℃ to obtain Ni (OH)2-a C composite material.
Reacting Ni (OH)2Placing the-C powder and sodium hypophosphite at the mass ratio of 1: 5 at two ends of a magnetic boat respectively, placing the magnetic boat in a tubular furnace, heating from room temperature to the target temperature of 300 ℃ at the heating rate of 3 ℃/min under the argon atmosphere, keeping the temperature constant for 2h, and carrying out phosphorization to obtain Ni2P-C composite material.
And (3) performance testing:
the materials obtained in example 1 and comparative examples 1 to 3 above were characterized and tested. Powder X-ray diffraction (XRD) patterns were measured using a bruker D8Advance tester. Scanning Electron Microscope (SEM) images were collected using Hitachi SU 8020. Transmission Electron Microscope (TEM) images were collected using JEM 1200 EX. The electrocatalytic activity was determined using the SP-50 electrochemical workstation from Bio-Logic, France. The performance of hydrogen evolution of electrolyzed water is tested by 0.5mol L-1 H2SO4As an electrolyte, 10mV S-1The linear sweep voltammetry test was performed. Accelerated stability test at 0.5mol L-1H2SO4As an electrolyte, with100mV S-1Linear scanning is performed at a rate of 3000 cycles.
FIG. 1 is an SEM topography of the cobalt-based metal organic framework compound with a dodecahedron structure obtained in step 1) of example 1, and it can be seen that the cobalt-based metal organic framework compound with the dodecahedron structure has a relatively uniform and regular morphology, shows a dodecahedron structure with clear edges and corners, and has an average particle size of about 600 nm.
FIG. 2 is the XRD pattern of Co-C of dodecahedral porous carbon composite material containing cobalt metal simple substance obtained in step 2) of example 1, from which obvious diffraction peak of simple substance cobalt can be seen, which shows that Co in cobalt-based metal organic framework compound increases with carbonization temperature2+The ions are gradually reduced and condensed into elemental cobalt particles. In addition, a diffraction peak of C is also present in the figure. The high-temperature treatment in the argon atmosphere ensures the formation of a cobalt simple substance in the porous carbon, thereby promoting Ni (OH) in the subsequent hydrothermal reaction2Nucleation within the porous carbon.
FIG. 3 is an SEM image of the dodecahedral porous carbon composite Co-C containing the cobalt metal simple substance obtained in step 2) of example 1. As can be seen from the figure, most of the particles retained the dodecahedral structure of the cobalt-based metal-organic framework compound obtained in step 1).
FIG. 4 shows the nanoscale Ni obtained in example 12XRD pattern of P-CoP-C bimetallic phosphide. The figure shows obvious CoP diffraction peaks and Ni2P diffraction peak. In addition, a diffraction peak of C is also present in the figure.
FIG. 5 shows the nanoscale Ni obtained in example 12TEM spectrum of P-CoP-C bimetal phosphide. It can be seen from the figure that the thin film uniformly covered with the porous carbon surface is replaced by densely distributed nanoparticles, and the small particles are separated without serious agglomeration.
FIG. 6 shows Ni obtained in example 12P-CoP-C and comparative examples Co-C, CoP-C, Ni2LSV patterns of electrolyzed water hydrogen evolution for P-C and commercial Pt-C catalysts. As can be seen from the figure, Ni is the most active2P-C-CoP-C material with an initial overpotential of 90mV and a current density of 10mA cm-2The corresponding overpotential is 160 mV. From which can be obtainedIt is seen that the bimetallic phosphide Ni2P-CoP-C relatively simple Ni2The HER catalytic activity of P-C or CoP-C is obviously better, Ni2The activity of P is improved by the synergistic effect of P and CoP.
FIG. 7 shows Ni obtained in example 12P-CoP-C at 0.5M H2SO4Polarization curves for 1 st and 3000 th rounds of cyclic voltammetric scans in solution. Comparing the intermediate initial potential and the overpotential of the first and last turns, it was found that the difference was very small, indicating that the activity of the material changed less, indicating that Ni is present2The P-CoP-C has good electrolytic water catalytic stability.
Claims (8)
1. A carbon-bimetallic phosphide composite material characterized in that: the composite material is composed of a carbon skeleton with a dodecahedron structure and bimetallic phosphide nanoparticles.
2. The carbon-bimetal phosphide composite material of claim 1, wherein: the carbon-bimetal phosphide composite material is Ni2P-CoP-C, wherein the bimetallic phosphide is Ni2P-CoP nanoparticles.
3. A method of preparing the carbon-bimetallic phosphide composite material as set forth in claim 1, characterized by the steps of:
1) weighing Co (NO) according to the mass ratio of 1: 1-33)2·6H2O and 2-methylimidazole, dissolving in 100ml methanol, stirring for dissolving, and adding Co (NO) into the 2-methylimidazole solution3)2Stirring the solution, aging the solution at room temperature for 24 hours after stopping stirring, and then centrifugally separating, cleaning and drying the product to obtain a cobalt-based metal organic framework compound with a dodecahedron structure;
2) placing the cobalt-based metal organic framework compound obtained in the step 1) into a quartz boat, placing the quartz boat into a tubular resistance furnace, heating to 550-900 ℃ in an argon atmosphere, and preserving heat for 1-8 hours to obtain a dodecahedral porous carbon composite material Co-C containing a cobalt metal simple substance;
3) adding the Co-C composite material obtained in the step 2) into NaOH solution for stirring, and adding Ni (NO) in the stirring process3)2The solution was added dropwise and stirred well. Pouring the uniformly stirred solution into a reaction kettle, heating to 100 ℃, preserving heat for 10-30h, cooling to room temperature, then centrifugally separating, cleaning and drying the product to obtain Ni (OH)2-Co-C powder;
4) reacting Ni (OH)2the-Co-C powder and the sodium hypophosphite are respectively arranged at two ends of the magnetic boat according to the mass ratio of 1: 5, the magnetic boat is arranged in a tubular furnace, the temperature is raised to 200-400 ℃ in the argon atmosphere, the temperature is kept for 0.5-4h for phosphorization, and the carbon-bimetal phosphide composite material Ni is obtained after the temperature is cooled to the room temperature2P-CoP-C。
4. The method of preparing a carbon-bimetallic phosphide composite material as set forth in claim 3, wherein: the cleaning and drying in the step 1) are carried out by washing for 3 times by using methanol and then vacuum drying for 8h at the temperature of 60 ℃.
5. The method of preparing a carbon-bimetallic phosphide composite material as set forth in claim 3, wherein: in the step 2), the temperature is raised to 600 ℃ at the temperature raising rate of 5 ℃/min, and the temperature is kept for 2 h.
6. The method of preparing a carbon-bimetallic phosphide composite material as set forth in claim 3, wherein: the concentration of the NaOH solution in the step 4) is 8mol/L, and the Ni (NO) is3)2The concentration of the solution was 0.05 mol/L.
7. Use of a carbon-bimetallic phosphide composite material as defined in one of claims 1 or 2 or a carbon-bimetallic phosphide composite material prepared by a method as defined in any one of claims 3 to 6, wherein: the carbon-bimetal phosphide composite material is applied to the field of electrocatalytic hydrogen production.
8. A catalyst material, characterized by: comprising the carbon-bimetallic phosphide composite material as set forth in one of claims 1 or 2.
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