CN110639565B - Carbon-bimetal phosphide composite material and preparation method thereof - Google Patents

Carbon-bimetal phosphide composite material and preparation method thereof Download PDF

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CN110639565B
CN110639565B CN201810675269.8A CN201810675269A CN110639565B CN 110639565 B CN110639565 B CN 110639565B CN 201810675269 A CN201810675269 A CN 201810675269A CN 110639565 B CN110639565 B CN 110639565B
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石佳子
许文才
李东立
付亚波
廖瑞娟
张新林
张柳鑫
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Beijing Institute of Graphic Communication
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    • 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
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Abstract

Carbon-bimetal phosphide composite Ni 2 The composite material is composed of a carbon skeleton with a dodecahedron structure and Ni 2 Bimetallic phosphide nanoparticles of P-CoP. Ni is prepared and obtained on a carbon skeleton matrix with a dodecahedron structure 2 P-CoP-C composite material, effective retention of dodecahedron structure carbon skeleton, ensuring Ni 2 P-CoP active substance particles are uniformly dispersed in a porous carbon matrix, so that agglomeration of the P-CoP active substance particles in the reaction process is prevented, effective exposure of Hydrogen Evolution Reaction (HER) active sites is promoted, and the catalytic activity of the material is improved; the carbon skeleton can effectively improve the conductivity of the whole catalyst material, thereby further improving the catalytic performance; the synergistic effect between the phases of the bimetallic phosphide plays an important role in improving the electrochemical catalytic performance.

Description

Carbon-bimetal phosphide composite material and preparation method thereof
Technical Field
The invention relates to a carbon-bimetal phosphide composite material Ni 2 P-CoP-C and 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. However, the existing serious cathode polarization problem greatly increases the energy consumption of the catalytic hydrogen production technology, thereby increasing the hydrogen production cost. Noble metals such as Pt and their alloys have the best electrocatalytic hydrogen evolution properties, but they are costly and difficult to apply on a large scale. The development of a high-performance low-cost non-noble metal catalyst has important significance for promoting the application of the electrocatalytic hydrogen production technology.
The 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 has been rapidly developed in recent years. Bimetallic phosphides have superior properties to monometallic phosphides due to the synergistic effect between different elements, which makes them ideal materials for replacing noble metal electrocatalysts. Junhua Song et al (Bimetallic Cobalt-Based Phosphide Zeolitic Imidazolate Framework: coPx Phase-Dependent Electrical Conductivity and Hydrogen Atom Adsorption Energy for Efficient Overall Water Splitting [ J ]. Adv.energy Mater.,2017,7, 1601555) synthesized cobalt-based bimetallic phosphide, and compared to cobalt-based bimetallic phosphide, the cobalt-based bimetallic phosphide was found to be more active than cobalt phosphide, indicating that the introduction of a second metal element was beneficial for enhancing the activity of the transition metal phosphide.
Disclosure of Invention
The invention aims to provide a carbon-bimetal phosphide Ni composite material of carbon-bimetal phosphide 2 The composite material is composed of a carbon skeleton with a dodecahedron structure and Ni 2 Bimetallic phosphide nanoparticles of P-CoP.
The shape, size and composition of the bimetal phosphide rechecking material have obvious influence on the electrocatalytic activity of the bimetal phosphide rechecking material, and the Ni is prepared and obtained on a carbon skeleton matrix with a dodecahedron structure 2 P-CoP-C composite material, effective retention of dodecahedron structure carbon skeleton, ensuring Ni 2 P-CoP active substance particles are uniformly dispersed in a porous carbon matrix, so that agglomeration of the P-CoP active substance particles in the reaction process is prevented, effective exposure of Hydrogen Evolution Reaction (HER) active sites is promoted, and the catalytic activity of the material is improved; (2) The carbon skeleton can effectively improve the conductivity of the whole catalyst material, thereby further improving the catalytic performance; (3) The synergistic effect between 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 1:1-3 3 ) 2 ·6H 2 O and 2-methylimidazole were dissolved in 100ml of methanol, and after stirring to dissolve, the 2-methylimidazole solution was poured into Co (NO 3 ) 2 Stirring in the solution, aging for 24 hours at room temperature after stopping stirring, and centrifugally separating, cleaning and drying the product to obtain the cobalt-based metal organic framework compound with the dodecahedron structure.
2) Placing the cobalt-based metal organic framework compound obtained in the step 1) into a quartz boat, placing into a tubular resistance furnace, heating to 550-900 ℃ under an argon atmosphere, and preserving heat for 1-8h to obtain the dodecahedron 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 to stir, and adding 3ml of Ni (NO) in the stirring process 3 ) 2 The 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, said powder being washed and dried;
4) Ni (OH) 2 Placing Co-C powder 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 200-400 ℃ under argon atmosphere, preserving heat for 0.5-4h for phosphating, and cooling to room temperature to obtain the carbon-bimetallic phosphide composite material Ni 2 P-CoP-C。
The washing and drying in the step 1) are carried out by adopting methanol for washing 3 times, and then vacuum drying is carried out for 8 hours at 60 ℃.
The temperature rise in the step 2) is to rise to 600 ℃ at a temperature rise rate of 5 ℃/min, and the temperature is kept for 2 hours.
The concentration of the NaOH solution in the step 4) is 8mol/L, and the Ni (NO) 3 ) 2 The concentration of the solution was 0.05mol/L.
The method of the invention has the following characteristics:
(1) The cobalt-containing product is obtained by carbonizing a cobalt-based metal organic framework compound having a dodecahedron structureDodecahedral porous carbon matrix material of simple substance and ensuring Ni after phosphating 2 The P-CoP active material particles are uniformly dispersed in the porous carbon matrix.
(2) Co-metal in carbon matrix promotes Ni (OH) together with hydrothermal environment 2 The core is formed in the porous carbon, and the growth of the micropores in the porous carbon is inhibited, so that the aggregation of particles is prevented, and the purposes of improving the specific surface area and enhancing the catalytic activity are achieved.
Drawings
Fig. 1 is an SEM topography of example 1 step 1) cobalt-based metal-organic framework compounds having a dodecahedral structure.
FIG. 2 is an XRD pattern of a dodecahedral porous carbon composite Co-C containing elemental cobalt metal obtained in step 2) of example 1
FIG. 3 is an SEM image of a dodecahedral porous carbon composite Co-C containing elemental cobalt metal obtained in step 2) of example 1.
FIG. 4 shows Ni obtained in example 1 2 XRD pattern of P-CoP-C bimetallic phosphide.
FIG. 5 is Ni obtained in example 1 2 TEM spectrum of P-CoP-C bimetallic phosphide.
FIG. 6 is Ni obtained in example 1 2 P-CoP-C and comparative Co-C, coP-C, ni 2 LSV profile of electrolyzed water hydrogen evolution for P-C and commercial Pt-C catalysts.
FIG. 7 is Ni obtained in example 1 2 P-CoP-C and comparative Co-C, coP-C, ni 2 Tafel profile of electrolyzed water hydrogen evolution for P-C and commercial Pt-C catalysts.
Detailed Description
Example 1
1) Weigh 0.498gCo (NO) 3 ) 2 ·6H 2 O and 0.656g of 2-methylimidazole were dissolved in 50ml of methanol, stirred for 10 minutes, and after dissolution by stirring, the 2-methylimidazole solution was rapidly poured into Co (NO) 3 ) 2 And (3) in the solution, continuing stirring for 10min, aging for 24h at room temperature after stopping stirring, centrifugally separating the product, washing 3 times with methanol, and finally drying at 60 ℃ in vacuum for 8h 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, and heating the quartz boat to a target temperature of 600 ℃ from room temperature at a heating rate of 5 ℃/min under argon atmosphere, and keeping the temperature constant for 2 hours to obtain the dodecahedron porous carbon composite material Co-C containing the cobalt metal simple substance.
3) The prepared 30mg of composite Co-C is placed in 10ml of deionized water, ultrasonic treatment is carried out until NO precipitate is generated, the composite Co-C is added into 20ml of NaOH solution with the concentration of 8mol/L, the mixture is stirred for 1h, and 3ml of Ni (NO) with the concentration of 0.05mol/L is added in the stirring process 3 ) 2 The solution was added dropwise and stirred well. Pouring the uniformly stirred solution into a 50mL reaction kettle liner, sealing and screwing the reaction kettle liner by using a steel shell, heating the reaction kettle liner to 100 ℃, preserving heat for 24 hours, cooling the reaction kettle liner to room temperature, washing and drying the reaction kettle liner by using ethanol and deionized water, and vacuum-drying the collected particles at 60 ℃ for 24 hours to obtain Ni (OH) 2 -Co-C powder.
4) Ni (OH) to be produced 2 Placing Co-C powder and sodium hypophosphite at the two ends of a magnetic boat according to the mass ratio of 1:5, 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 argon atmosphere, and phosphating for 2 hours constantly, and cooling to room temperature to obtain the carbon-bimetal phosphide composite material Ni 2 P-CoP-C。
Example 2
1) Synthesis of cobalt-based metal organic framework compounds with dodecahedral structure: weigh 1gCo (NO) 3 ) 2 ·6H 2 O and 3g of 2-methylimidazole were dissolved in 800ml of methanol, respectively, and stirred for 10 minutes, after which the 2-methylimidazole solution was rapidly poured into Co (NO) 3 ) 2 And (3) in the solution, continuing stirring for 10min, aging for 12h at room temperature after stopping stirring, centrifugally separating the product, washing 3 times with methanol, and finally drying at 60 ℃ in vacuum for 12h 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, and heating the quartz boat from room temperature to a target temperature of 800 ℃ at a heating rate of 5 ℃/min under argon atmosphere, and keeping the temperature constant for 4 hours to obtain the dodecahedron porous carbon composite material Co-C containing the cobalt metal simple substance.
3) The prepared 40mg of composite Co-C was placed in 10ml of deionized water and sonicated until there was NO precipitate, and it was added to 30ml of NaOH solution at a concentration of 8mol/L and stirred for 1h, during which 4ml of Ni (NO) at a concentration of 0.08mol/L was added 3 ) 2 The solution was added dropwise and stirred well. Pouring the uniformly stirred solution into a 50mL reaction kettle liner, sealing and screwing the reaction kettle liner by using a steel shell, heating the reaction kettle liner to 80 ℃, preserving heat for 12 hours, cooling the reaction kettle liner to room temperature, washing and drying the reaction kettle liner by using ethanol and deionized water, and vacuum-drying the collected particles at 60 ℃ for 24 hours to obtain Ni (OH) 2 -Co-C powder.
4) Ni (OH) to be produced 2 Placing Co-C powder and sodium hypophosphite at the two ends of a magnetic boat according to the mass ratio of 1:4, placing the magnetic boat in a tubular furnace, heating from room temperature to the target temperature of 350 ℃ at the heating rate of 5 ℃/min under argon atmosphere, and phosphating for 3 hours constantly, and cooling to room temperature to obtain the carbon-bimetal phosphide composite material Ni 2 P-CoP-C。
Comparative example 1
The dodecahedral porous carbon composite material Co-C containing the cobalt metal simple substance obtained in the step 2) of example 1 was used as an electrocatalytic comparison material.
Comparative example 2
Phosphating the obtained dodecahedron porous carbon composite material Co-C containing the cobalt metal simple substance in the step 2) of the embodiment 1, respectively placing the Co-C composite material and sodium hypophosphite at the 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 ℃ under argon atmosphere, preserving heat for 2 hours for phosphating, and cooling to room temperature to obtain the carbon-metal phosphide composite material CoP-C.
Comparative example 3
Placing the dodecahedron porous carbon composite material Co-C containing the cobalt metal simple substance obtained in the step 2) in an HF aqueous solution, stirring for 24 hours to remove Co, cleaning and collecting by deionized water, and drying for 24 hours at 60 ℃ in vacuum to obtain the porous carbon C-HF treated by HF acid.
The prepared 30mg of porous carbon C-HF was placed in 10ml of deionized water and added to 20ml of deionized water until the solution was uniformly precipitated-free, and the concentration wasStirring in 8mol/L NaOH solution for 1h, during which 3ml of 0.05mol/L Ni (NO) 3 ) 2 The solution was added dropwise and stirred well. Pouring the uniformly stirred solution into a 50mL reaction kettle liner, sealing and screwing the reaction kettle liner by using a steel shell, heating the reaction kettle liner to 100 ℃, preserving heat for 24 hours, cooling the reaction kettle liner to room temperature, washing and drying the reaction kettle liner by using ethanol and deionized water, collecting particles, and vacuum-drying the particles at 60 ℃ for 24 hours to obtain Ni (OH) 2 -C composite material.
Ni (OH) 2 Placing the powder C at two ends of a magnetic boat according to the mass ratio of 1:5 and sodium hypophosphite, placing the magnetic boat in a tubular furnace, heating from room temperature to the target temperature 300 ℃ at the heating rate of 3 ℃/min under argon atmosphere, and phosphating for 2 hours to obtain Ni 2 P-C composite materials.
Performance test:
the materials obtained in example 1, comparative examples 1-3 above were characterized and tested. Powder X-ray diffraction (XRD) patterns were measured using a bruck D8Advance tester. Scanning Electron Microscopy (SEM) images were acquired using Hitachi SU 8020. Transmission Electron Microscopy (TEM) images were acquired using JEM 1200 EX. Electrocatalytic activity was measured using an electrochemical workstation of the SP-50 type from Bio-Logic company, france. Electrolytic Water Hydrogen evolution Performance test at 0.5mol L -1 H 2 SO 4 As an electrolyte, at 10mV S -1 Is subjected to linear sweep voltammetry testing. Accelerated stability test at 0.5mol L -1 H 2 SO 4 As an electrolyte, 100mV S -1 Is scanned linearly for 3000 cycles.
Fig. 1 is an SEM morphology diagram of the cobalt-based metal-organic framework compound having a dodecahedron structure in step 1) of example 1, and it can be seen from the figure that the cobalt-based metal-organic framework compound having a dodecahedron structure has a relatively uniform and regular morphology, exhibits a dodecahedron structure with distinct edges and corners, and has an average particle diameter of about 600 nm.
FIG. 2 is an XRD pattern of a dodecahedral porous carbon composite Co-C containing elemental cobalt obtained in step 2) of example 1, from which a distinct elemental cobalt diffraction peak is seen, indicating Co in a cobalt-based metal organic framework compound with increasing carbonization temperature 2+ The ions are gradually reduced and condensed into elemental cobalt particles. In addition, there is a diffraction peak of C in the figure. The high-temperature treatment in the argon atmosphere ensures the formation of cobalt simple substance in the porous carbon, thereby promoting Ni (OH) in the subsequent hydrothermal reaction 2 Nucleation inside the porous carbon.
FIG. 3 is an SEM image of a dodecahedral porous carbon composite Co-C containing elemental cobalt metal obtained in step 2) of example 1. It can be seen from the figure that most of the particles retain the dodecahedral structure of the cobalt-based metal organic framework compound obtained in step 1).
FIG. 4 shows the nano-scale Ni obtained in example 1 2 XRD pattern of P-CoP-C bimetallic phosphide. In the figure, there are obvious CoP diffraction peaks and Ni 2 P diffraction peak. In addition, there is a diffraction peak of C in the figure.
FIG. 5 shows the nano-scale Ni obtained in example 1 2 TEM spectrum of P-CoP-C bimetallic phosphide. As can be seen from the figure, the thin film uniformly covered on the porous carbon surface is replaced by densely distributed nanoparticles, and the small particles are separated without serious agglomeration.
FIG. 6 is Ni obtained in example 1 2 P-CoP-C and comparative Co-C, coP-C, ni 2 LSV profile of electrolyzed water hydrogen evolution for P-C and commercial Pt-C catalysts. As can be seen from the graph, ni is the most active 2 P-C-CoP-C material with an initial overpotential of 90mV and a current density of 10mA cm -2 The corresponding overpotential was 160mV. It can be seen that the bimetallic phosphide Ni 2 P-CoP-C is more unitary than Ni 2 The HER catalytic activity of P-C or CoP-C is obviously better, ni 2 The synergistic effect of P and CoP increases the activity.
FIG. 7 is Ni obtained in example 1 2 P-CoP-C at 0.5M H 2 SO 4 Polarization curves for circle 1 and 3000 of cyclic voltammetry scans were performed in solution. Comparing the mid-onset and over-potential of the first and last turns, the difference was found to be very small, indicating that the material activity was changing less, indicating that Ni 2 The P-CoP-C has good electrolytic water catalytic stability.

Claims (4)

1. Use of a carbon-bimetallic phosphide composite material characterized by: the carbon-bimetal phosphide composite material is applied to the field of electrocatalytic hydrogen production;
the composite material is composed of a carbon skeleton with a dodecahedron structure and bimetallic phosphide nano-particles;
the composite material is Ni 2 P-CoP-C, wherein the bimetallic phosphide is Ni 2 P-CoP nanoparticles;
the preparation method of the carbon-bimetal phosphide composite material comprises the following steps:
1) Weighing Co (NO) according to the mass ratio of 1:1-3 3 ) 2 ·6H 2 O and 2-methylimidazole are then dissolved in 100mL of methanol, and after stirring to dissolve, the 2-methylimidazole solution is poured into Co (NO 3 ) 2 Stirring in the solution, aging for 24 hours at room temperature after stopping stirring, and centrifugally separating, cleaning and drying the product to obtain the cobalt-based metal organic framework compound with the dodecahedron structure;
2) Placing the cobalt-based metal organic framework compound obtained in the step 1) into a quartz boat, placing into a tubular resistance furnace, heating to 550-900 ℃ under an argon atmosphere, and preserving heat for 1-8h to obtain a dodecahedron 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 to stir, and adding Ni (NO) in the stirring process 3 ) 2 Dropwise adding the solution, stirring, pouring the stirred solution into a reaction kettle, heating to 100deg.C, maintaining the temperature for 10-30 hr, cooling to room temperature, centrifuging, cleaning, and drying to obtain Ni (OH) 2 -Co-C powder;
4) Ni (OH) 2 Placing Co-C powder 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 200-400 ℃ under argon atmosphere, preserving heat for 0.5-4h for phosphating, and cooling to room temperature to obtain the carbon-bimetallic phosphide composite material Ni 2 P-CoP-C。
2. Use of the carbon-bimetallic phosphide composite as set forth in claim 1, characterized in that: the washing and drying in the step 1) are carried out by adopting methanol for washing 3 times, and then vacuum drying is carried out for 8 hours at 60 ℃.
3. Use of the carbon-bimetallic phosphide composite as set forth in claim 1, characterized in that: the temperature rise in step 2) is to rise to 600 ℃ at a temperature rise rate of 5 ℃/min, and the temperature is kept for 2h.
4. Use of the carbon-bimetallic phosphide composite as set forth in claim 1, characterized in that: the concentration of the NaOH solution in step 3) was 8mol/L, and the Ni (NO) 3 ) 2 The concentration of the solution was 0.05mol/L.
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