CN113583248B - Highly-crosslinked phosphorus-doped one-dimensional amorphous metal organic framework nanowire network material and preparation method and application thereof - Google Patents

Highly-crosslinked phosphorus-doped one-dimensional amorphous metal organic framework nanowire network material and preparation method and application thereof Download PDF

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CN113583248B
CN113583248B CN202110889843.1A CN202110889843A CN113583248B CN 113583248 B CN113583248 B CN 113583248B CN 202110889843 A CN202110889843 A CN 202110889843A CN 113583248 B CN113583248 B CN 113583248B
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张晓伟
韩梦夷
赵智勇
王鹏
陈晓
巴肖华
唐雪
王戈
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Beijing Normal University
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Abstract

The invention relates to the field of electrocatalytic materials, in particular to a highly crosslinked phosphorus-doped one-dimensional amorphous metal organic framework nanowire network material and a preparation method and application thereof. The preparation method provided by the invention comprises the following steps: mixing soluble metal salt, organic ligand, strong base and water, and carrying out hydrothermal reaction to obtain a one-dimensional metal organic framework nanowire; performing thermal non-crystallization treatment on the one-dimensional metal organic framework nanowire to obtain a highly-crosslinked one-dimensional amorphous metal organic framework nanowire network structure; and carrying out phosphating treatment on the highly crosslinked one-dimensional amorphous metal organic framework nanowire network structure to obtain the highly crosslinked phosphorus-doped one-dimensional amorphous metal organic framework nanowire network material. The highly crosslinked phosphorus-doped one-dimensional amorphous metal organic framework nanowire network material prepared by the preparation method has better electrocatalytic activity and electrocatalytic stability.

Description

Highly-crosslinked phosphorus-doped one-dimensional amorphous metal organic framework nanowire network material and preparation method and application thereof
Technical Field
The invention relates to the field of electrocatalytic materials, in particular to a highly crosslinked phosphorus-doped one-dimensional amorphous metal organic framework nanowire network material and a preparation method and application thereof.
Background
The fuel cell is named as green and environment-friendly energy of 21 century and is listed as the first of ten technologies in the world in the future. A fuel cell is an energy conversion device that directly converts chemical energy stored in fuel into electrical energy through an electrochemical reaction without using a heat engine to do work. By converting intermittent renewable energy sources such as solar energy, wind energy, etc. into chemical energy that can be used as fuel for fuel cells, efficient storage, transportation, and conversion of renewable energy sources can be greatly facilitated.
There are many kinds of fuel cells such as Proton Exchange Membrane Fuel Cells (PEMFCs), Direct Methanol Fuel Cells (DMFCs), Alkaline Fuel Cells (AFCs), phosphoric acid type fuel cells (PAFCs), Molten Carbonate Fuel Cells (MCFCs), and Solid Oxide Fuel Cells (SOFCs). The PEMFC and the DMFC respectively use hydrogen and methanol as fuels and oxygen as an oxidant, and have wider prospects due to the advantages of simple system structure, easy storage of fuels, low use temperature and the like.
The direct methanol fuel cell uses methanol as fuel, oxygen as oxidant, and the products of complete reaction are carbon dioxide and water. When the two electrodes are connected by an external circuit, CH3OH and O2Respectively generating electrochemical Reaction at the anode and cathode, and Methanol Oxidation Reaction (MOR) at the anode, CH3Oxidation of OH molecules to CO2Generation of protons (H)+) Passes through the proton exchange membrane to reach the cathode, and simultaneously emits 6 electrons to form current from the current passing through an external circuit to the cathode, and finally, the current passes through the cathode and H+And O2Recombination to form H2And O. MOR is a six-electron reaction, the reaction process is complex, and a plurality of intermediates are used, so that the MOR is a speed-determining step in the DMFC process and determines the performance and output power of the DMFC, and therefore, the MOR catalyst has important significance for researching the MOR process catalyst.
At present, research on the MOR catalyst mainly focuses on Pt and other noble metal-based catalysts, because Pt has very good catalytic performance for MOR, but the defects in the art are that the yield of the Pt-based catalyst is scarce and the price is high, and because the Pt has too strong adsorption capacity for MOR intermediate CO, an active site is easily and firmly adsorbed by CO in the MOR catalytic process, so that the active site is shielded and subsequent catalysis cannot be continued, which is called as the CO poisoning effect of the Pt-based catalyst, so that the stability of the Pt-based catalyst is poor, and the wider application of the Pt-based catalyst is influenced. Therefore, research into a low-cost, high-activity and stable catalyst that can replace the Pt-based catalyst is crucial.
The Metal-Organic Frameworks (MOFs) are novel nano porous materials, are three-dimensional materials with special pore channel structures formed by self-assembling Metal ions and polydentate Organic ligands (mainly aromatic carboxylic acids), have important applications in the fields of adsorption separation, gas storage, drug slow release and the like due to rich structures, large specific surface areas and various pore channels, but for the field of catalysis, the traditional three-dimensional MOFs are mostly in micrometer scale, and Metal nodes and micropore pore diameters at the atomic level are not favorable for substrate diffusion. However, in recent years, researches on low-dimensional MOFs find that the low-dimensional structure reduces mass transfer resistance caused by a microporous structure in the three-dimensional MOFs, is beneficial to absorption and desorption of reaction intermediate species and transmission of electrons, and can effectively improve catalytic activity in an electrocatalysis process. Although the low-dimensional MOFs can take full advantage of the structural advantages of the MOFs, the conductivity of the low-dimensional MOFs is inherently insufficient, and the interface resistance of the low-dimensional MOFs still limits the conductivity and mass transfer capability of the low-dimensional MOFs, and the low-dimensional MOFs still cannot meet the optimal requirements, so that how to further improve the MOFs-based materials and improve the reaction activity of the MOFs-based materials is still a great challenge.
Disclosure of Invention
The invention aims to provide a highly crosslinked phosphorus-doped one-dimensional amorphous metal organic framework nanowire network material, and a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a highly crosslinked phosphorus-doped one-dimensional amorphous metal organic framework nanowire network material, which comprises the following steps:
mixing soluble metal salt, organic ligand, strong base and water, and carrying out hydrothermal reaction to obtain a one-dimensional metal organic framework nanowire;
performing thermal non-crystallization treatment on the one-dimensional metal organic framework nanowire to obtain a highly-crosslinked one-dimensional amorphous metal organic framework nanowire network structure;
and carrying out phosphating treatment on the highly crosslinked one-dimensional amorphous metal organic framework nanowire network structure to obtain the highly crosslinked phosphorus-doped one-dimensional amorphous metal organic framework nanowire network material.
Preferably, the soluble metal salt comprises one or more of soluble nickel salt, soluble cobalt salt, soluble iron salt, soluble copper salt, soluble manganese salt and soluble vanadium salt.
Preferably, the organic ligand comprises one or more of 4,4' -biphenyl dicarboxylic acid, 1, 2-dimethyl imidazole, methyl imidazole, terephthalic acid and trimesic acid.
Preferably, the molar ratio of the soluble metal salt to the organic ligand is 1: (0.1-5).
Preferably, the hydrothermal reaction has a pH = 11-14, a temperature of 160-220 ℃, and a time of 12 h.
Preferably, the thermal amorphization treatment is carried out in an inert atmosphere;
the temperature of the thermal non-crystallizing treatment is 300-500 ℃, and the time is 0.5-5 h.
Preferably, the process of the phosphating treatment comprises the following steps:
placing a phosphorus source at the upwind position of a tubular furnace, placing the highly crosslinked one-dimensional amorphous metal organic framework nanowire network structure at the downwind position of the tubular furnace, and introducing protective gas for phosphating;
the mass ratio of the highly crosslinked one-dimensional amorphous metal organic framework nanowire network structure to the phosphorus source is 1: (10-40).
Preferably, the temperature of the phosphating treatment is 300-500 ℃ and the time is 0.5-5 h.
The invention also provides a highly crosslinked phosphorus-doped one-dimensional amorphous metal organic framework nanowire network material prepared by the preparation method in the technical scheme, which comprises a highly crosslinked one-dimensional amorphous metal organic framework nanowire network structure and phosphorus elements uniformly doped in the highly crosslinked one-dimensional amorphous metal organic framework nanowire network structure.
The invention also provides the application of the highly crosslinked phosphorus-doped one-dimensional amorphous metal organic framework nanowire network material in a fuel cell.
The invention provides a preparation method of a highly crosslinked phosphorus-doped one-dimensional amorphous metal organic framework nanowire network material, which comprises the following steps: mixing soluble metal salt, organic ligand, strong base and water, and carrying out hydrothermal reaction to obtain one-dimensional Metal Organic Framework Nanowires (MOFNWs); carrying out thermal non-crystallization treatment on the one-dimensional Metal Organic Framework Nanowire (MOFNWs) to obtain a highly cross-linked one-dimensional amorphous metal organic framework nanowire network structure (a-MOFNWs); and carrying out phosphating treatment on the highly crosslinked one-dimensional amorphous metal organic framework nanowire network structure (a-MOFNWs) to obtain the highly crosslinked phosphorus-doped one-dimensional amorphous metal organic framework nanowire network material (a-MOFNWs-P). The invention realizes the amorphization treatment of the one-dimensional metal organic framework nanowire through the thermotropic amorphization treatment, the invention constructs a highly crosslinked and one-dimensional metal organic framework nanowire network structure with a large number of vacancy defects after the thermotropic amorphization treatment, constructs a highly crosslinked nanowire network while introducing the defects, and the separated nanowires are mutually crosslinked under the action of the thermotropic amorphization treatment to obtain the network structure, thereby effectively reducing the interface resistance in the electrocatalysis process, prolonging the electron transmission channel and promoting the gas release; and then, in-situ phosphorus element doping is carried out on the one-dimensional amorphous metal organic framework nanowire network structure, the interface regulation of an a-MOFNWs cross-linked network is carried out by the phosphorus element, and the electronic structure of a metal active center is optimized on an atomic level, so that the adsorption energy of metal sites to oxygen-containing species is optimized, the electrochemical activity of the metal organic framework derivative is further improved, and the prepared catalyst has better electrocatalytic activity and stability.
Drawings
FIG. 1 is a schematic flow diagram of the present invention for preparing the highly cross-linked phosphor-doped one-dimensional amorphous metal-organic framework nanowire network material;
FIG. 2 is an SEM picture of NiCo (1:5) -MOFNWs as described in example 1;
FIG. 3 is an SEM picture of a-NiCo (1:5) -MOFNWs-390 as described in example 1;
FIG. 4 is an SEM photograph of a-NiCo (1:5) -MOFNWs-390-P as described in example 1;
FIG. 5 is an XRD plot of NiCo (1:5) -MOFNWs, a-NiCo (1:5) -MOFNWs-390, and a-NiCo (1:5) -MOFNWs-390-P as described in example 1;
FIG. 6 is the EDS energy spectrum of a-NiCo (1:5) -MOFNWs-390-P described in example 1;
FIG. 7 is a CV curve of a-NiCo (1:5) -MOFNWs-390-P in NaOH solution and NaOH & methanol mixed solution, respectively, according to example 1;
FIG. 8 is an XRD pattern of Co-MOFNWs, a-Co-MOFNWs-420, and a-Co-MOFNWs-420-P as described in example 2;
FIG. 9 is the EDS energy spectrum of a-Co-MOFNWs-420-P described in example 2;
FIG. 10 is a comparison of CV curves for Co-MOFNWs, a-Co-MOFNWs-420, and a-Co-MOFNWs-420-P as described in example 2;
FIG. 11 is a graph comparing CV curves of Co-MOFNWs of example 2 before and after 10 cycles;
FIG. 12 is a graph comparing CV curves of a-Co-MOFNWs-420-P of example 2 before and after 1000 cycles.
Detailed Description
The invention provides a preparation method of a highly crosslinked phosphorus-doped one-dimensional amorphous metal organic framework nanowire network material, which comprises the following steps:
mixing soluble metal salt, organic ligand, strong base and water, and carrying out hydrothermal reaction to obtain a one-dimensional metal organic framework nanowire;
performing thermal non-crystallization treatment on the one-dimensional metal organic framework nanowire to obtain a highly-crosslinked one-dimensional amorphous metal organic framework nanowire network structure;
and carrying out phosphating treatment on the highly crosslinked one-dimensional amorphous metal organic framework nanowire network structure to obtain the highly crosslinked phosphorus-doped one-dimensional amorphous metal organic framework nanowire network material.
In the present invention, all the starting materials for the preparation are commercially available products known to those skilled in the art unless otherwise specified.
The invention mixes soluble metal salt, organic ligand, strong base and water to carry out hydrothermal reaction, and obtains the one-dimensional metal organic framework nanowire.
In the present invention, the mixing preferably comprises the steps of:
mixing soluble metal salt with part of water to obtain a solution A;
mixing the organic ligand, strong base and residual water to obtain a solution B;
mixing the solution A and the solution B.
The invention mixes the soluble metal salt and part of water to obtain solution A.
In the invention, the soluble metal salt preferably comprises one or more of soluble nickel salt, soluble cobalt salt, soluble iron salt, soluble copper salt, soluble manganese salt and soluble vanadium salt; the soluble nickel salt preferably comprises nickel nitrate and/or nickel chloride; the soluble cobalt salt preferably comprises cobalt nitrate and/or cobalt chloride; the soluble ferric salt preferably comprises one or more of ferrous nitrate, ferric nitrate, ferrous chloride and ferric chloride; the soluble copper salt preferably comprises copper nitrate; the soluble manganese salt preferably comprises manganese nitrate and/or manganese chloride; the soluble vanadium salt preferably comprises vanadium trichloride; when the soluble metal salt is more than two of the specific choices, the proportion of the specific substances is not limited in any way, and the soluble metal salt can be mixed according to any proportion. In a specific embodiment of the invention, the soluble metal salt is a mixture of nickel nitrate and cobalt nitrate in a molar ratio of 1:5, a mixture of nickel nitrate and cobalt nitrate in a molar ratio of 1:20, a mixture of nickel nitrate and cobalt nitrate in a molar ratio of 1:10, or cobalt nitrate;
in the present invention, the molar concentration of the solution A is preferably 0.01 to 1 mmol/mL, and more preferably 0.1 to 0.5 mmol/mL.
The mixing of the soluble metal salt and part of water is not limited in any way, and the mixing is carried out by adopting the process well known to the skilled person in the art and can ensure that the obtained solution A is uniformly mixed.
The organic ligand, strong base and residual water are mixed to obtain solution B.
In the present invention, the organic ligand preferably comprises one or more of 4,4' -biphenyldicarboxylic acid, 1, 2-dimethylimidazole, methylimidazole, terephthalic acid and trimesic acid; when the organic ligands are more than two of the specific choices, the proportion of the specific substances is not limited in any way, and the specific substances can be mixed according to any proportion. In a specific embodiment of the invention, the organic ligand is 4,4' -biphenyldicarboxylic acid.
In the present invention, the strong base is preferably an alkali metal hydroxide, more preferably sodium hydroxide.
In the invention, the molar ratio of the organic ligand to the strong base is preferably 1 (1-5), and more preferably 1 (1-3).
In the present invention, the molar concentration of the solution B is preferably 0.01 to 1 mmol/mL, more preferably 0.01 to 0.5mmol/mL, and most preferably 0.05 to 0.15 mmol/mL.
The present invention does not have any particular limitation on the mixing of the organic ligand, the strong base and the remaining water, and may be carried out by a process well known to those skilled in the art and ensure uniform mixing.
In the present invention, the molar ratio of the soluble metal salt to the organic ligand is preferably 1: (0.1 to 5), more preferably 1: (0.2 to 2), most preferably 1: (0.5 to 1.5).
In the invention, the pH value of the hydrothermal reaction is preferably 11-14, and more preferably 12-13.
In the invention, the temperature of the hydrothermal reaction is preferably 160-220 ℃, more preferably 170-210 ℃, and most preferably 195-205 ℃; the time is preferably 12 h.
In the present invention, the hydrothermal reaction is preferably carried out in a hydrothermal reaction kettle; the ratio of the volume of the reaction system in which the hydrothermal reaction takes place to the volume of the hydrothermal reaction tank is preferably 70: 100.
After the one-dimensional metal organic framework nanowire is obtained, the one-dimensional metal organic framework nanowire is subjected to thermal non-crystallization treatment to obtain a highly-crosslinked one-dimensional amorphous metal organic framework nanowire network structure.
In the present invention, the thermal amorphization treatment is preferably carried out in an inert atmosphere; the inert atmosphere used in the present invention is not particularly limited, and those known to those skilled in the art can be used.
In the invention, the temperature of the thermal non-crystallizing treatment is preferably 300-500 ℃, more preferably 350-450 ℃, and most preferably 380-420 ℃; the time is preferably 0.5 to 5 hours, more preferably 1 to 4.3 hours, and most preferably 1 to 2 hours.
After the thermally induced amorphization treatment, the present invention preferably further comprises cooling; the cooling process is not particularly limited in the present invention, and may be performed by a process known to those skilled in the art.
After the highly crosslinked one-dimensional amorphous metal organic framework nanowire network structure is obtained, the highly crosslinked one-dimensional amorphous metal organic framework nanowire network structure is subjected to phosphating treatment to obtain the highly crosslinked phosphorus-doped one-dimensional amorphous metal organic framework nanowire network material.
In the present invention, the process of the phosphating treatment is preferably: placing a phosphorus source at the upwind position of a tubular furnace, placing the highly crosslinked one-dimensional amorphous metal organic framework nanowire network structure at the downwind position of the tubular furnace, and introducing protective gas for phosphating; the mass ratio of the highly crosslinked one-dimensional amorphous metal organic framework nanowire network structure to the phosphorus source is preferably 1: (10-40), more preferably 1: (13-32), most preferably 1: (18-26).
In the present invention, the kind of the shielding gas is preferably nitrogen, argon or helium.
In the present invention, the phosphorus source is preferably NaH2PO2Or NH4H2PO2More preferably NaH2PO2。
In the invention, the introducing speed of the protective gas is preferably 10-50 mL/min, and more preferably 20 mL/min.
In the invention, the temperature of the phosphating treatment is preferably 300-500 ℃, more preferably 350-450 ℃, and most preferably 380-420 ℃; the time is preferably 0.5 to 5 hours, more preferably 1 to 4.3 hours, and most preferably 1 to 2 hours.
The invention also provides a highly crosslinked phosphorus-doped one-dimensional amorphous metal organic framework nanowire network material prepared by the preparation method in the technical scheme, which comprises a highly crosslinked one-dimensional amorphous metal organic framework nanowire network structure and phosphorus elements uniformly doped in the highly crosslinked one-dimensional amorphous metal organic framework nanowire network structure.
The invention also provides the application of the highly crosslinked phosphorus-doped one-dimensional amorphous metal organic framework nanowire network material in a fuel cell. In the invention, the highly crosslinked phosphorus-doped one-dimensional amorphous metal organic framework nanowire network material is preferably used as an electrocatalyst in a fuel cell; the method of the present invention is not particularly limited, and the method may be performed by a method known to those skilled in the art.
The highly crosslinked phosphorus doped one-dimensional amorphous metal organic framework nanowire network material provided by the present invention, the preparation method and the application thereof are described in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
Example 1
The preparation is carried out according to the scheme shown in figure 1: 0.0969g of Ni (NO) according to the molar ratio of 1:53)2·6H2O and 0.4850g of Co (NO)3)2·6H2Dissolving O in 10 mL of aqueous solution, fully mixing to obtain a solution A, dissolving 0.4845g of 4,4' -biphenyldicarboxylic acid and 0.16g of NaOH in 25mL of water, fully mixing to obtain a solution B, quickly adding the solution A into the solution B, stirring for 1h under a high-speed magnetic stirring state, transferring into a reaction kettle, carrying out hydrothermal reaction for 12h at 200 ℃, washing, centrifuging and drying to obtain pink one-dimensional NiCo (1:5) metal organic framework nanowires (marked as NiCo (1:5) -MOWFNs);
carrying out thermal amorphization on the NiCo (1:5) -MOFNWs for 1h at 390 ℃ in a nitrogen atmosphere to obtain a black powdery highly-crosslinked one-dimensional amorphous metal organic framework nanowire network (marked as a-NiCo (1:5) -MOFNWs-390);
in a tube furnace, 600mg NaH was added2PO2Placing the nano-wire network material at an upwind position, placing 30mg of the a-NiCo (1:5) -MOFNWs-390 at a downwind position, introducing nitrogen at a nitrogen introduction rate of 20 mL/min, and carrying out phosphating treatment at a temperature of 390 ℃ for 1h to obtain the black powdery highly-crosslinked phosphorus-doped one-dimensional amorphous metal organic framework nano-wire network material (marked as a-NiCo (1:5) -MOFNWs-390-P);
SEM tests are respectively carried out on the materials, and the test results are shown in a figure 2 (NiCo (1:5) -MOFNWs), a figure 3 (a-NiCo (1:5) -MOFNWs-390) and a figure 4 (a-NiCo (1:5) -MOFNWs-390-P), and as can be seen from figures 2-4, the NiCo (1:5) -MOFNWs are in one-dimensional nanowire shapes, and the a-NiCo (1:5) -MOFNWs-390-P are in highly cross-linked one-dimensional nanowire network structures;
XRD tests are carried out on the NiCo (1:5) -MOFNWs, a-NiCo (1:5) -MOFNWs-390 and a-NiCo (1:5) -MOFNWs-390-P, the test results are shown in figure 5, as can be seen from figure 5, the XRD of the NiCo (1:5) -MOFNWs has typical crystal structure characteristic peaks of a metal organic framework, the a-NiCo (1:5) -MOFNWs-390 after thermal amorphization treatment has an amorphous structure without obvious crystal structure characteristic peaks, and the a-NiCo (1:5) -MOFNWs-390-P also has no obvious XRD crystal peaks and proves that no other crystal structures grow after phosphorization.
EDS (electron-ray diffraction) spectrum test is carried out on the a-NiCo (1:5) -MOFNWs-390-P, the test result is shown in figure 6, as can be seen from figure 6, the EDS spectrum test of the a-NiCo (1:5) -MOFNWs-390-P shows that the elements of Ni, Co, C, O and P exist, XRD has no metal phosphide crystal peak, and the EDS spectrum has the existence of P element, which proves that the phosphorus element is doped on the a-NiCo (1:5) -MOFNWs-390;
the a-NiCo (1:5) -MOFNWs-390-P material is prepared into electrode solution (catalyst (a-NiCo (1:5) -MOFNWs-390-P): 2mg, water: 495 muL, ethanol: 495 muL, Nafion solution: 10 muL), and loaded on a glassy carbon electrode (the load is 0.2 mg cm)-2) The electrochemical catalytic methanol oxidation performance test is carried out by taking the electrochemical catalytic methanol oxidation performance test as a working electrode, and the test process is as follows: three-electrode system: reference: an Ag/AgCl electrode; counter electrode: a graphite electrode; a working electrode: a glassy carbon electrode; electrolyte solution: 0.5M NaOH + 0.5M methanol solution; 0.5M NaOH; an electrochemical workstation: princeton PMC 1000&2000；Scan rate：10mV·s-1；
The results are shown in FIG. 7, in which FIG. 7 is an electrocatalytic methanol oxidation CV curve of the a-NiCo (1:5) -MOFNWs-390-P, and it can be seen from FIG. 7 that in the electrolyte solution after adding 0.5M methanol to 0.5M NaOH solution, the current density of the a-NiCo (1:5) -MOFNWs-390-P is controlled from 2.89 mA-cm at a voltage of 1.6V (vs RHE)-2Increased to 78.7 mA cm-2The a-NiCo (1:5) -MOFNWs-390-P is proved to have good electrocatalytic activity on methanol.
Example 2
The preparation is carried out according to the scheme shown in figure 1: 0.5821g of Co (NO)3)2·6H2Dissolving O in 10 mL of water to obtain a solution A, dissolving 0.4845g of 4,4' -biphenyldicarboxylic acid and 0.16g of NaOH in 25mL of water to obtain a solution B, quickly adding the solution A into the solution B, stirring for 1h under a high-speed magnetic stirring state, transferring into a reaction kettle, and carrying out hydrothermal reaction for 12h at 200 ℃ to obtain pink one-dimensional Co metal organic framework nanowires (marked as Co-MOFNWs);
performing thermal non-crystallization treatment on the Co-MOFNWs for 1h at the temperature of 420 ℃ in a nitrogen atmosphere to obtain a black powdery highly-crosslinked one-dimensional amorphous metal organic framework nanowire network structure (marked as a-Co-MOFNWs-420);
in a tube furnace, 600mg NaH was added2PO2Placing the material at the upwind position, placing 30mg of the a-Co-MOFNWs-420 at the downwind position, introducing nitrogen at the nitrogen introduction rate of 20 mL/min, and carrying out phosphating treatment at the temperature of 420 ℃ for 1h to obtain the black powdery highly-crosslinked phosphorus-doped one-dimensional amorphous metal organic framework nanowire network material (marked as a-Co-MOFNWs-420-P);
XRD tests are carried out on the Co-MOFNWs, a-Co-MOFNWs-420 and a-Co-MOFNWs-420-P, the test results are shown in figure 8, as can be seen from figure 8, XRD of the Co-MOFNWs has a characteristic peak of a typical crystal structure of a metal organic framework, a-Co-MOFNWs subjected to thermal non-crystallization treatment is in an amorphous structure, no characteristic peak of the obvious crystal structure exists, no obvious XRD crystal peak exists in the a-Co-MOFNWs-420-P, and it is proved that no other crystal structures grow after phosphorization.
EDS energy spectrum test is carried out on the a-Co-MOFNWs-420-P, the test result is shown in figure 9, as can be seen from figure 9, the EDS energy spectrum of the a-Co-MOFNWs-420-P detects the existence of Co, C, O and P elements, XRD has no metal phosphide crystal peaks, and the EDS energy spectrum has the existence of P elements, which proves that the phosphorus elements are doped on the a-Co-MOFNWs-420;
the Co-MOFNWs, a-Co-MOFNWs-420 and a-Co-MOFNWs-420-P materials are prepared into electrode solution (catalyst (Co-MOFNWs, a-Co-MOFNWs-420 and a-Co-MOFNWs-420-P): 2mg, water: 495 muL, ethanol: 495 muL and Nafion solution: 10 muL) which is loaded on a glassy carbon electrode (the load is 0.2 mg cm)-2) The electrochemical catalytic methanol oxidation performance test is carried out by taking the electrochemical catalytic methanol oxidation performance test as a working electrode, and the test process is as follows: three-electrode system: reference: an Ag/AgCl electrode; counter electrode: a graphite electrode; a working electrode: a glassy carbon electrode; electrolyte solution: 0.5M NaOH + 0.5M methanol solution; 0.5M NaOH; an electrochemical workstation: princeton PMC 1000&2000；Scan rate：10mV·s-1；
The test results are shown in FIG. 10It can be seen that the electrocatalytic methanol oxidation performance of Co-MOFNWs is effectively improved after the thermal amorphous networking post-treatment and the secondary phosphating treatment, and the corresponding current densities of the Co-MOFNWs, a-Co-MOFNWs-420 and a-Co-MOFNWs-420-P after 10 CV electrochemical activation are respectively 0.286 mA-cm-2，15.1 mA·cm-2，30.9 mA·cm-2The current densities of a-Co-MOFNWs-420 and a-Co-MOFNWs-420-P were increased by about 53 times and 108 times, respectively, relative to Co-MOFNWs.
FIG. 11 is a graph of CV cycles of the Co-MOFNWs at 1 st and 10 th cycles, with a current density of 10.2 mA cm at 1.6V (vs RHE) for the Co-MOFNWs at 1 st CV cycle-2On the other hand, when the current density is increased to the 10 th CV, the current density is only 0.286 mA cm-2And the performance loss is 97.2%, which proves that the Co-MOFNWs nanowire has poor electrocatalytic methanol oxidation stability, and FIG. 12 shows that the current density of the a-Co-MOFNWs-420-P is 30.9 mA-cm at 1.6V (vs RHE) at the 1 st CV cycle curve of the a-Co-MOFNWs-420-P at the first CV cycle curve and the 1000 th CV cycle curve-2And the current density at the 1000 th CV was 21.5 mA cm-2The performance loss is only 30.4%, and as can be seen from fig. 12, the a-Co-MOFNWs-420-P after the thermal amorphous network treatment and the secondary phosphating treatment has stronger stability in the electrochemical methanol oxidation reaction process.
Example 3
The preparation is carried out according to the scheme shown in figure 1: 0.0277g of Ni (NO) according to the molar ratio of 1:203)2·6H2O and 0.5543g of Co (NO)3)2·6H2Dissolving O in 10 mL of aqueous solution, fully mixing to obtain a solution A, then fully mixing with 0.4845g of 4,4' -biphenyldicarboxylic acid and 0.16g of NaOH in 25mL of water to obtain a solution B, quickly adding the solution A into the solution B for mixing, then stirring for 1h under a high-speed magnetic stirring state, transferring into a reaction kettle, carrying out hydrothermal reaction for 12h at 200 ℃, washing, centrifuging and drying to obtain pink one-dimensional NiCo (1:20) metal organic framework nanowires (marked as NiCo (1:20) -MOWFNs);
carrying out thermal amorphization on the NiCo (1:20) -MOFNWs for 1.5h at the temperature of 400 ℃ in a nitrogen atmosphere to obtain a highly-crosslinked one-dimensional amorphous metal organic framework nanowire network (marked as a-NiCo (1:20) -MOFNWs-400);
in a tube furnace, 900mg NaH was added2PO2And (2) placing the nano-wire network material at an upwind position, placing 30mg of the a-NiCo (1:20) -MOFNWs-400 at a downwind position, introducing nitrogen at the nitrogen introduction rate of 20 ml/min, and carrying out phosphating treatment at the temperature of 400 ℃ for 1h to obtain the black powdery highly-crosslinked phosphorus-doped one-dimensional amorphous metal organic framework nano-wire network material (marked as a-NiCo (1:20) -MOFNWs-400-P).
Example 4
The preparation is carried out according to the scheme shown in figure 1: 0.0529g of Ni (NO) according to the molar ratio of 1:103)2·6H2O and 0.5291g of Co (NO)3)2·6H2Dissolving O in 10 mL of aqueous solution, fully mixing to obtain a solution A, then fully mixing with 0.4845g of 4,4' -biphenyldicarboxylic acid and 0.16g of NaOH dissolved in 25mL of water to obtain a solution B, quickly adding the solution A into the solution B for mixing, then stirring for 1h under a high-speed magnetic stirring state, transferring into a reaction kettle, carrying out hydrothermal reaction for 12h at 200 ℃, washing, centrifuging and drying to obtain pink one-dimensional NiCo (1:10) metal organic framework nanowires (marked as NiCo (1:10) -MOFNWs);
carrying out thermal amorphization on the NiCo (1:10) -MOFNWs for 1.5h at the temperature of 410 ℃ in a nitrogen atmosphere to obtain a highly-crosslinked one-dimensional amorphous metal organic framework nanowire network (marked as a-NiCo (1:10) -MOFNWs-410);
in a tube furnace, 1200mg NaH was added2PO2And (2) placing the nano-wire network material at an upwind position, placing 30mg of the a-NiCo (1:10) -MOFNWs-410 at a downwind position, introducing nitrogen at the nitrogen introduction rate of 20 ml/min, and carrying out phosphating treatment at the temperature of 410 ℃ for 1h to obtain the black powdery highly-crosslinked phosphorus-doped one-dimensional amorphous metal organic framework nano-wire network material (marked as a-NiCo (1:10) -MOFNWs-410-P).
The results of the tests for electrocatalytic activity and electrocatalytic stability of example 3 and example 4 are similar to those of example 1 and example 2.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the present invention, and these improvements and modifications should also be construed as the protection scope of the present invention.

Claims (4)

1. A preparation method of a highly cross-linked phosphorus-doped one-dimensional amorphous metal organic framework nanowire network material is characterized by comprising the following steps:
mixing soluble metal salt, organic ligand, strong base and water, and carrying out hydrothermal reaction to obtain a one-dimensional metal organic framework nanowire;
performing thermal non-crystallization treatment on the one-dimensional metal organic framework nanowire to obtain a highly-crosslinked one-dimensional amorphous metal organic framework nanowire network structure;
carrying out phosphating treatment on the highly crosslinked one-dimensional amorphous metal organic framework nanowire network structure to obtain the highly crosslinked phosphorus-doped one-dimensional amorphous metal organic framework nanowire network material;
the soluble metal salt comprises soluble nickel salt and/or soluble cobalt salt;
the organic ligand comprises one or more of 4,4' -biphenyl dicarboxylic acid, terephthalic acid and trimesic acid;
the molar ratio of the soluble metal salt to the organic ligand is 1: (0.1-5);
the hydrothermal reaction is carried out at the pH = 11-14, the temperature of 160-220 ℃ and the time of 12 h;
the thermal non-crystallization treatment is carried out in an inert atmosphere;
the temperature of the thermal non-crystallizing treatment is 300-500 ℃, and the time is 0.5-5 h;
the temperature of the phosphating treatment is 300-500 ℃, and the time is 0.5-5 h.
2. The method of claim 1, wherein the phosphating process comprises:
placing a phosphorus source at the upwind position of a tubular furnace, placing the highly crosslinked one-dimensional amorphous metal organic framework nanowire network structure at the downwind position of the tubular furnace, and introducing protective gas for phosphating;
the mass ratio of the highly crosslinked one-dimensional amorphous metal organic framework nanowire network structure to the phosphorus source is 1: (10-40).
3. The highly cross-linked phosphorus-doped one-dimensional amorphous metal-organic framework nanowire network material prepared by the preparation method of claim 1 or 2, which comprises a highly cross-linked one-dimensional amorphous metal-organic framework nanowire network structure and phosphorus uniformly doped in the highly cross-linked one-dimensional amorphous metal-organic framework nanowire network structure.
4. Use of the highly crosslinked phosphorus doped one dimensional amorphous metal organic framework nanowire network material of claim 3 in a fuel cell.
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