CN114400339A - Heteropoly acid @ MOFs/polymer electrostatic spinning nanofiber - Google Patents

Heteropoly acid @ MOFs/polymer electrostatic spinning nanofiber Download PDF

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CN114400339A
CN114400339A CN202111476549.4A CN202111476549A CN114400339A CN 114400339 A CN114400339 A CN 114400339A CN 202111476549 A CN202111476549 A CN 202111476549A CN 114400339 A CN114400339 A CN 114400339A
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mofs
polymer
electrostatic spinning
heteropoly acid
pom
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CN114400339B (en
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牛其建
王涛
陆宇豪
王雪婧
王承建
董秀秀
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Jiangsu University
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Abstract

The invention relates to the technical field of electrochemical catalysis, and particularly relates to heteropoly acid @ MOFs/polymer electrostatic spinning nanofiber. MOFs easily cause structural collapse in the carbonization process, so that active particles are seriously agglomerated, and the full play of the electro-catalytic performance of the catalyst is limited. Based on the problems, the invention provides heteropoly acid @ MOFs/polymer electrostatic spinning nanofiber, which adopts the double-confinement effect of MOFs material and high-molecular polymer electrostatic spinning fiber to encapsulate transition metal and hetero atoms, reduces the agglomeration phenomenon among nano particles, improves the distribution condition of metal nano particles in a catalyst material, and fully exerts the electrocatalysis performance of the obtained composite catalyst.

Description

Heteropoly acid @ MOFs/polymer electrostatic spinning nanofiber
Technical Field
The invention relates to the technical field of electrochemical catalysis, and particularly relates to heteropoly acid @ MOFs/polymer electrostatic spinning nanofiber.
Background
The oxygen reduction and oxygen evolution reaction (ORR/OER) is the core reaction of numerous new energy conversion and storage devices (fuel cells, metal-air batteries and water electrolysis devices). However, the two types of reactions have slow kinetics and need to be catalyzed to be efficiently carried out.
The ORR/OER dual-function catalyst mainly comprises: noble metal catalysts, transition metal catalysts, carbon material catalysts and composite material catalysts thereof. The noble metal catalyst has high cost and poor stability and is difficult to realize large-scale commercial application. Transition metal catalysts are limited by poor electrical conductivity, often requiring the incorporation of electron donors (metal nanoparticles) or conductive materials (carbon or metal support materials). In addition, carbon materials doped with heteroatoms (N, P, S) have received much attention due to their advantages of high conductivity, porous structure, high thermal and chemical stability, etc. The transition metal catalyst is compounded with a carbon material, and the development of a novel high-efficiency electrocatalyst becomes a hotspot of research.
However, the preparation of ORR/OER bifunctional catalysts with porous structure and high activity components by combining transition metal catalysts with heteroatom-doped carbon materials through a simple process remains a challenge. Because the composition, the structure and the size of the precursor cannot be accurately regulated, insufficient and uneven exposure of catalytic active sites is easily caused, and the characteristics of adjustable morphology, composition and structure of metal-organic framework polymers (MOFs) prove that the metal-organic framework polymers are a novel precursor for preparing the transition metal/heteroatom-doped porous carbon material composite catalyst. However, the MOFs easily cause structural collapse in the carbonization process, so that the agglomeration of active particles is serious, and the full play of the electro-catalytic performance of the catalyst is limited.
Disclosure of Invention
Aiming at the problems in the prior art, the technical problems to be solved by the invention are as follows: MOFs easily cause structural collapse in the carbonization process, so that active particles are seriously agglomerated, and the full play of the electro-catalytic performance of the catalyst is limited.
The technical scheme adopted by the invention for solving the technical problems is as follows: the invention provides heteropoly acid @ MOFs/polymer electrostatic spinning nanofiber, which is prepared by the following steps:
(1) encapsulating heteropoly acid (POM) by using MOFs material hole confinement to obtain POM @ MOFs composite nanoparticles;
(2) loading the POM @ MOFs composite nanoparticles in the polymer nanofiber by using an electrostatic spinning technology to obtain a POM @ MOFs/polymer nanofiber precursor;
(3) and controlling a carbonization mode, and realizing in-situ doping of transition metal and hetero atoms on the POM @ MOFs/polymer nanofiber precursor to obtain the heteropoly acid @ MOFs/polymer electrostatic spinning nanofiber.
Specifically, the MOFs material is ZIF-8 or ZIF-67.
Specifically, the POM is H3PMo12O40、H3PW12O40And mixtures thereof.
Specifically, the polymer is PAN, PVA, PVP or PS.
Specifically, the step (1) is specifically performed according to the following steps:
the preparation method comprises the steps of taking a small-molecule organic ligand, soluble metal salt and heteropoly acid as initial raw materials, and adopting a solvothermal method to realize the confinement encapsulation of POM in MOFs pores to prepare the POM @ MOFs composite nanoparticles.
Specifically, the step (2) is specifically performed according to the following steps:
the POM @ MOFs/polymer composite nanofiber precursor is obtained by taking a high-molecular polymer, POM @ MOFs composite nanoparticles and an organic solvent as initial raw materials and adopting a coaxial electrostatic spinning technology.
Specifically, the technological parameters of the electrostatic spinning technology are as follows: electrostatic spinning voltage is 15-20 KV; the receiving distance is 15-20 cm; the advancing speed is 0.5ml/h, and the diameter of the spinning needle is 0.6 mm.
Specifically, the step (3) is specifically performed according to the following steps:
placing the POM @ MOFs/polymer nanofiber precursor in a vacuum tube furnace, firstly carrying out low-temperature pre-oxidation treatment in the air, then raising the temperature to 800 ℃ under the protection of Ar gas, and introducing an active atmosphere (H)2、H2O or H2S), preserving heat for 2h, and realizing synchronous high-temperature carbonization and in-situ phase conversion to obtain the heteropoly acid @ MOFs/polymer electrostatic spinning nanofiber.
Specifically, the low-temperature pre-oxidation treatment is to heat up to 280 ℃/min at the speed of 2 ℃/min in the air atmosphere and keep the temperature for 2 h.
The invention has the beneficial effects that:
the invention provides heteropoly acid @ MOFs/polymer electrostatic spinning nanofiber, which adopts double confinement effects of MOFs materials and high polymer electrostatic spinning fibers to encapsulate transition metals and heteroatoms, reduces the agglomeration phenomenon among nanoparticles, improves the distribution condition of metal nanoparticles in a catalyst material, provides a high-conductivity electron transmission channel, and can fully exert the electrocatalytic performance of the obtained composite catalyst.
Drawings
FIG. 1: ORR electrocatalytic properties of POM @ MOFs/polymer electrospun nanofibers obtained in example 1.
FIG. 2: OER electrocatalytic properties of POM @ MOFs/polymer electrospun nanofibers obtained in example 1.
Detailed Description
The present invention will now be described in further detail with reference to the accompanying drawings.
The low-temperature pre-oxidation treatment in the following embodiment of the invention is to heat up to 280 ℃/min at the rate of 2 ℃/min in the air atmosphere and keep the temperature for 2 h.
Example 1
(1) First of all, preparation of H3PW12O40@ ZIF-8 composite nanoparticles
1.125g of Zn (NO)3)2 6H2Zinc O nitrate was dissolved in 100mL of deionized water, and 1.113g H was added thereto3PW12O40To be dispersedAfter the mixture is uniform, 13.75g of 2-methylimidazole is added into the solution, the mixture is stirred and reacted for 24 hours at room temperature, the mixture is centrifuged and washed by deionized water for three times, and H is obtained3PW12O40@ ZIF-8 composite nano particles are put into a vacuum drying oven to be dried for later use;
(2) followed by preparation of H3PW12O40@ ZIF-8/PAN electrostatic spinning nanofiber precursor
0.5g PAN and 0.5g H3PW12O40@ ZIF-8 composite nanoparticles are simultaneously added into 4.5g of DMF solution, and stirred to form uniform solution; then, a high-voltage electrostatic spinning machine is utilized to set electrostatic spinning parameter voltage of 20KV, the receiving distance is 20cm, the advancing speed is 0.5ml/H, the diameter of a spinning needle head is 0.6mm, and H is formed by spinning3PW12O40@ ZIF-8/PAN electrospun nanofiber precursor;
(3) finally, for the obtained H3PW12O40@ ZIF-8/PAN electrostatic spinning nanofiber precursor is subjected to high-temperature carbonization and in-situ phase transformation
H obtained in the step (2)3PW12O40@ ZIF-8/PAN electrostatic spinning nanofiber precursor is placed in a vacuum tube furnace, firstly low-temperature preoxidation treatment is carried out in the air, then the temperature rising rate is 10 ℃/min, under the protection of Ar gas, when the temperature rises to 800 ℃, active atmosphere H is introduced2S, preserving the heat for 2h to obtain the POM @ MOFs/polymer electrostatic spinning nanofiber.
Example 2
(1) First of all, preparation of H3PMo12O40@ ZIF-8 composite nanoparticles
1.125g of Zn (NO)3)2 6H2Zinc O nitrate was dissolved in 100mL of deionized water, and 1.113g H was added thereto3PMo12O40After the solution is uniformly dispersed, 13.75g of 2-methylimidazole is added into the solution, the mixture is stirred and reacted for 24 hours at room temperature, and the mixture is centrifuged and washed by deionized water for three times to obtain H3PMo12O40@ ZIF-8 composite nano particles are put into a vacuum drying oven and dried for later use;
(2) followed by preparation of H3PMo12O40@ ZIF-8/PAN electrostatic spinning nanofiber precursor
0.5g PAN and 0.5g H3PMo12O40The @ ZIF-8 composite nano particles are simultaneously added into 4.5g of DMF solution, stirred to form uniform solution, and then a high-voltage electrostatic spinning machine is utilized to set electrostatic spinning parameter voltage of 20 KV; the receiving distance is 20 cm; the advancing speed is 0.5 ml/h; the diameter of the spinning needle is 0.6mm, and H is prepared3PMo12O40@ ZIF-8/PAN electrospun nanofiber precursor;
(3) finally, for the obtained H3PMo12O40@ ZIF-8/PAN electrostatic spinning nanofiber precursor is subjected to high-temperature carbonization and in-situ phase transformation (active atmosphere H)2S)
H obtained in the step (2)3PMo12O40@ ZIF-8/PAN electrostatic spinning nanofiber precursor is placed in a vacuum tube furnace, firstly low-temperature preoxidation treatment is carried out in the air, then the temperature rising rate is 10 ℃/min, under the protection of Ar gas, when the temperature rises to 800 ℃, active atmosphere H is introduced2S, preserving the heat for 2h to obtain the POM @ MOFs/polymer electrostatic spinning nanofiber.
Example 3
(1) First of all, preparation of H3PW12O40@ ZIF-67 composite nanoparticles
1.125g of Co (NO)3)2 6H2Cobalt O nitrate was dissolved in 100mL of deionized water, and 1.113g H was added thereto3PW12O40After the solution is uniformly dispersed, 13.75g of 2-methylimidazole is added into the solution, the mixture is stirred and reacted for 24 hours at room temperature, and the mixture is centrifuged and washed by deionized water for three times to obtain H3PW12O40@ ZIF-67 composite nano particles are put into a vacuum drying oven to be dried for later use;
(2) followed by preparation of H3PW12O40@ ZIF-67/PAN electrospun nanofiber precursor
0.5g PAN and 0.5g H3PW12O40@ ZIF-67 composite nanoparticles were simultaneously added to 4.5g of DMF solution, stirred to form a homogeneous solution, and thenThen setting an electrostatic spinning parameter voltage of 15KV by using a high-voltage electrostatic spinning machine; the receiving distance is 15 cm; the advancing speed is 0.5 ml/h; the diameter of the spinning needle is 0.6mm, and H is prepared3PW12O40@ ZIF-67/PAN electrospun nanofiber precursor;
(3) finally, for the obtained H3PW12O40@ ZIF-67/PAN electrostatic spinning nanofiber precursor is subjected to high-temperature carbonization and in-situ phase transformation
H obtained in the step (2)3PW12O40@ ZIF-67/PAN electrostatic spinning nanofiber precursor is placed in a vacuum tube furnace, firstly, low-temperature pre-oxidation treatment is carried out in the air, and then the heating rate is 10 ℃/min; under the protection of Ar gas, when the temperature is raised to 800 ℃, introducing active atmosphere H2S, preserving the heat for 2h to obtain the POM @ MOFs/polymer electrostatic spinning nanofiber.
Example 4
(1) First of all, preparation of H3PMo12O40@ ZIF-67 composite nanoparticles
1.125g of Co (NO)3)2 6H2Cobalt O nitrate was dissolved in 100mL of deionized water, and 1.113g H was added thereto3PMo12O40After the solution is uniformly dispersed, 13.75g of 2-methylimidazole is added into the solution, the mixture is stirred and reacted for 24 hours at room temperature, and the mixture is centrifuged and washed by deionized water for three times to obtain H3PMo12O40@ ZIF-67 composite nano particles are put into a vacuum drying oven and dried for later use;
(2) followed by preparation of H3PMo12O40@ ZIF-67/PAN electrospun nanofiber precursor
0.5g PAN and 0.5g H3PMo12O40The @ ZIF-67 composite nano particles are simultaneously added into 4.5g of DMF solution, stirred to form uniform solution, and then a high-voltage electrostatic spinning machine is utilized to set electrostatic spinning parameter voltage of 20 KV; the receiving distance is 20 cm; the advancing speed is 0.5 ml/h; the diameter of the spinning needle is 0.6mm, and H is prepared3PMo12O40@ ZIF-67/PAN electrospun nanofiber precursor;
(3) finally, the pair is obtainedH of (A) to (B)3PMo12O40@ ZIF-67/PAN electrostatic spinning nanofiber precursor is subjected to high-temperature carbonization and in-situ phase transformation
H obtained in the step (2)3PMo12O40@ ZIF-67/PAN electrostatic spinning nanofiber precursor is placed in a vacuum tube furnace, firstly, low-temperature pre-oxidation treatment is carried out in the air, and then the heating rate is 10 ℃/min more; under the protection of Ar gas, when the temperature is raised to 800 ℃, introducing active atmosphere H2S, preserving heat for 2 hours; thus obtaining the POM @ MOFs/polymer electrostatic spinning nanofiber.
Example 5
(1) First of all, preparation of H3PW12O40@ ZIF-8 composite nanoparticles
1.125g of Zn (NO)3)2 6H2Zinc O nitrate was dissolved in 100mL of deionized water, and 1.113g H was added thereto3PW12O40After the solution is uniformly dispersed, adding 13.75g of 2-methylimidazole into the solution, stirring and reacting for 24 hours at room temperature, centrifuging and washing for three times by using deionized water to obtain H3PW12O40@ ZIF-8 composite nano particles are put into a vacuum drying oven to be dried for later use;
(2) followed by preparation of H3PW12O40@ ZIF-8/PAN electrostatic spinning nanofiber precursor
0.5g PAN and 0.5g H3PW12O40@ ZIF-8 composite nanoparticles are simultaneously added into 4.5g of DMF solution, and stirred to form uniform solution; then, a high-voltage electrostatic spinning machine is utilized to set electrostatic spinning parameter voltage of 20KV, the receiving distance is 20cm, the advancing speed is 0.5ml/H, the diameter of a spinning needle head is 0.6mm, and H is formed by spinning3PW12O40@ ZIF-8/PAN electrospun nanofiber precursor;
(3) finally, for the obtained H3PW12O40@ ZIF-8/PAN electrostatic spinning nanofiber precursor is subjected to high-temperature carbonization and in-situ phase transformation
H obtained in the step (2)3PW12O40@ ZIF-8/PAN electrostatic spinning nanofiber precursor is placed in a vacuum tubeIn the formula furnace, firstly low-temperature preoxidation treatment is carried out in the air, then the temperature rising rate is 10 ℃/min, under the protection of Ar gas, when the temperature rises to 800 ℃, active atmosphere H is introduced2And keeping the temperature for 2h to obtain the POM @ MOFs/polymer electrostatic spinning nanofiber.
Example 6
(1) First of all, preparation of H3PW12O40@ ZIF-8 composite nanoparticles
1.125g of Zn (NO)3)2 6H2Zinc O nitrate was dissolved in 100mL of deionized water, and 1.113g H was added thereto3PW12O40After the solution is uniformly dispersed, adding 13.75g of 2-methylimidazole into the solution, stirring and reacting for 24 hours at room temperature, centrifuging and washing for three times by using deionized water to obtain H3PW12O40@ ZIF-8 composite nano particles are put into a vacuum drying oven to be dried for later use;
(2) followed by preparation of H3PW12O40@ ZIF-8/PAN electrostatic spinning nanofiber precursor
0.5g PAN and 0.5g H3PW12O40@ ZIF-8 composite nanoparticles are simultaneously added into 4.5g of DMF solution, and stirred to form uniform solution; then, a high-voltage electrostatic spinning machine is utilized to set electrostatic spinning parameter voltage of 20KV, the receiving distance is 20cm, the advancing speed is 0.5ml/H, the diameter of a spinning needle head is 0.6mm, and H is formed by spinning3PW12O40@ ZIF-8/PAN electrospun nanofiber precursor;
(3) finally, for the obtained H3PW12O40@ ZIF-8/PAN electrostatic spinning nanofiber precursor is subjected to high-temperature carbonization and in-situ phase transformation
H obtained in the step (2)3PW12O40@ ZIF-8/PAN electrostatic spinning nanofiber precursor is placed in a vacuum tube furnace, firstly low-temperature preoxidation treatment is carried out in the air, then the temperature rising rate is 10 ℃/min, under the protection of Ar gas, when the temperature rises to 800 ℃, active atmosphere H is introduced2And O, keeping the temperature for 2h to obtain the POM @ MOFs/polymer electrostatic spinning nanofiber.
Example 7
(1) First of all, preparation of H3PW12O40@ ZIF-8 composite nanoparticles
1.125g of Zn (NO)3)2 6H2Zinc O nitrate was dissolved in 100mL of deionized water, and 1.113g H was added thereto3PW12O40After the solution is uniformly dispersed, adding 13.75g of 2-methylimidazole into the solution, stirring and reacting for 24 hours at room temperature, centrifuging and washing for three times by using deionized water to obtain H3PW12O40@ ZIF-8 composite nano particles are put into a vacuum drying oven to be dried for later use;
(2) followed by preparation of H3PW12O40@ ZIF-8/PVA electrospun nanofiber precursor
0.5g of PVA and 0.5g H3PW12O40@ ZIF-8 composite nanoparticles are simultaneously added into 4.5g of DMF solution, and stirred to form uniform solution; then, a high-voltage electrostatic spinning machine is utilized to set electrostatic spinning parameter voltage of 20KV, the receiving distance is 20cm, the advancing speed is 0.5ml/H, the diameter of a spinning needle head is 0.6mm, and H is formed by spinning3PW12O40@ ZIF-8/PAN electrospun nanofiber precursor;
(3) finally, for the obtained H3PW12O40@ ZIF-8/PVA electrospun nanofiber precursor for high-temperature carbonization and in-situ phase conversion
H obtained in the step (2)3PW12O40@ ZIF-8/PVA electrostatic spinning nanofiber precursor is placed in a vacuum tube furnace, firstly low-temperature preoxidation treatment is carried out in the air, then the temperature rising rate is 10 ℃/min, under the protection of Ar gas, when the temperature rises to 800 ℃, active atmosphere H is introduced2S, preserving the heat for 2h to obtain the POM @ MOFs/polymer electrostatic spinning nanofiber.
Example 8
(1) First of all, preparation of H3PW12O40@ ZIF-8 composite nanoparticles
1.125g of Zn (NO)3)2 6H2Zinc O nitrate was dissolved in 100mL of deionized water, and 1.113g H was added thereto3PW12O40After the solution is uniformly dispersed, adding 13.75g of 2-methylimidazole into the solution, stirring and reacting for 24 hours at room temperature, centrifuging and washing for three times by using deionized water to obtain H3PW12O40@ ZIF-8 composite nano particles are put into a vacuum drying oven to be dried for later use;
(2) followed by preparation of H3PW12O40@ ZIF-8/PVP electrostatic spinning nanofiber precursor
0.5g of PVP and 0.5g H3PW12O40@ ZIF-8 composite nanoparticles are simultaneously added into 4.5g of DMF solution, and stirred to form uniform solution; then, a high-voltage electrostatic spinning machine is utilized to set electrostatic spinning parameter voltage of 20KV, the receiving distance is 20cm, the advancing speed is 0.5ml/H, the diameter of a spinning needle head is 0.6mm, and H is formed by spinning3PW12O40@ ZIF-8/PVP electrospun nanofiber precursor;
(3) finally, for the obtained H3PW12O40@ ZIF-8/PVP electrostatic spinning nano-fiber precursor is subjected to high-temperature carbonization and in-situ phase transformation
H obtained in the step (2)3PW12O40@ ZIF-8/PVP electrostatic spinning nanofiber precursor is placed in a vacuum tube furnace, low-temperature pre-oxidation treatment is carried out in air firstly, then the temperature rising rate is 10 ℃/min, under the protection of Ar gas, when the temperature rises to 800 ℃, active atmosphere H is introduced2S, preserving the heat for 2h to obtain the POM @ MOFs/polymer electrostatic spinning nanofiber.
Example 9
(1) First of all, preparation of H3PW12O40@ ZIF-8 composite nanoparticles
1.125g of Zn (NO)3)2 6H2Zinc O nitrate was dissolved in 100mL of deionized water, and 1.113g H was added thereto3PW12O40After the solution is uniformly dispersed, adding 13.75g of 2-methylimidazole into the solution, stirring and reacting for 24 hours at room temperature, centrifuging and washing for three times by using deionized water to obtain H3PW12O40@ ZIF-8 composite nano particles are put into a vacuum drying oven to be dried for later use;
(2) followed by preparation of H3PW12O40@ ZIF-8/PS electrostatic spinning nanofiber precursor
0.5g of PS and 0.5g H3PW12O40@ ZIF-8 composite nanoparticles are simultaneously added into 4.5g of DMF solution, and stirred to form uniform solution; then, a high-voltage electrostatic spinning machine is utilized to set electrostatic spinning parameter voltage of 20KV, the receiving distance is 20cm, the advancing speed is 0.5ml/H, the diameter of a spinning needle head is 0.6mm, and H is formed by spinning3PW12O40@ ZIF-8/PS electrospinning nanofiber precursor;
(3) finally, for the obtained H3PW12O40@ ZIF-8/PS electrostatic spinning nano-fiber precursor is subjected to high-temperature carbonization and in-situ phase transformation
H obtained in the step (2)3PW12O40@ ZIF-8/PS electrostatic spinning nanofiber precursor is placed in a vacuum tube furnace, firstly low-temperature preoxidation treatment is carried out in the air, then the temperature rising rate is 10 ℃/min, under the protection of Ar gas, when the temperature rises to 800 ℃, active atmosphere H is introduced2S, preserving the heat for 2h to obtain the POM @ MOFs/polymer electrostatic spinning nanofiber.
Example 10
(1) Firstly, preparing composite heteropoly acid @ ZIF-8 composite nano particles
1.125g of Zn (NO)3)2 6H2Zinc O nitrate was dissolved in 100mL of deionized water, and 1.113g of a heteropoly acid which was H was added thereto3PW12O40And H3PMo12O40After the mixture is uniformly dispersed, adding 13.75g of 2-methylimidazole into the solution, stirring and reacting for 24 hours at room temperature, centrifuging and washing for three times by using deionized water to obtain composite heteropoly acid @ ZIF-8 composite nanoparticles, and putting the composite heteropoly acid @ ZIF-8 composite nanoparticles into a vacuum drying oven to be dried for later use;
(2) then preparing a composite heteropoly acid @ ZIF-8/PAN electrostatic spinning nanofiber precursor
Adding 0.5g of PAN and 0.5g of composite heteropoly acid @ ZIF-8 composite nano particle into 4.5g of DMF solution at the same time, and stirring to form uniformThe solution of (1); then, a high-voltage electrostatic spinning machine is utilized to set electrostatic spinning parameter voltage of 20KV, the receiving distance is 20cm, the advancing speed is 0.5ml/H, the diameter of a spinning needle head is 0.6mm, and H is formed by spinning3PW12O40@ ZIF-8/PAN electrospun nanofiber precursor;
(3) finally, carrying out high-temperature carbonization and in-situ phase transformation on the obtained composite heteropoly acid @ ZIF-8/PAN electrostatic spinning nanofiber precursor
Placing the composite heteropoly acid @ ZIF-8/PAN electrostatic spinning nanofiber precursor obtained in the step (2) in a vacuum tube furnace, firstly carrying out low-temperature pre-oxidation treatment in the air, then introducing active atmosphere H when the temperature is raised to 800 ℃ at the heating rate of 10 ℃/min under the protection of Ar gas2And S, preserving the heat for 2 hours to obtain the composite heteropoly acid/polymer electrostatic spinning nanofiber.
Example 11
(1) Firstly, preparing composite heteropoly acid @ ZIF-8 composite nano particles
1.125g of Zn (NO)3)2 6H2Zinc O nitrate was dissolved in 100mL of deionized water, and 1.113g of a heteropoly acid which was H was added thereto3PW12O40And H3PMo12O40After the mixture is uniformly dispersed, adding 13.75g of 2-methylimidazole into the solution, stirring at room temperature for reaction for 24 hours, centrifuging and washing with deionized water for three times to obtain composite heteropoly acid @ ZIF-8 composite nanoparticles, and putting the composite heteropoly acid @ ZIF-8 composite nanoparticles into a vacuum drying oven for drying for later use;
(2) then preparing a composite heteropoly acid @ ZIF-8/PAN electrostatic spinning nanofiber precursor
Adding 0.5g of PAN and 0.5g of composite heteropoly acid @ ZIF-8 composite nano particles into 4.5g of DMF solution at the same time, and stirring to form a uniform solution; then, a high-voltage electrostatic spinning machine is utilized to set electrostatic spinning parameter voltage of 20KV, the receiving distance is 20cm, the advancing speed is 0.5ml/H, the diameter of a spinning needle head is 0.6mm, and H is formed by spinning3PW12O40@ ZIF-8/PAN electrospun nanofiber precursor;
(3) finally, carrying out high-temperature carbonization and in-situ phase transformation on the obtained composite heteropoly acid @ ZIF-8/PAN electrostatic spinning nanofiber precursor
Placing the composite heteropoly acid @ ZIF-8/PAN electrostatic spinning nanofiber precursor obtained in the step (2) in a vacuum tube furnace, firstly carrying out low-temperature pre-oxidation treatment in the air, then introducing active atmosphere H when the temperature is raised to 800 ℃ at the heating rate of 10 ℃/min under the protection of Ar gas2And S, preserving the heat for 2 hours to obtain the composite heteropoly acid/polymer electrostatic spinning nanofiber.
Example 12
(1) Firstly, preparing composite heteropoly acid @ ZIF-8 composite nano particles
1.125g of Zn (NO)3)2 6H2Zinc O nitrate was dissolved in 100mL of deionized water, and 1.113g of a heteropoly acid which was H was added thereto3PW12O40And H3PMo12O40After the mixture is uniformly dispersed, adding 13.75g of 2-methylimidazole into the solution, stirring and reacting for 24 hours at room temperature, centrifuging and washing for three times by using deionized water to obtain composite heteropoly acid @ ZIF-8 composite nanoparticles, and putting the composite heteropoly acid @ ZIF-8 composite nanoparticles into a vacuum drying oven to be dried for later use;
(2) then preparing a composite heteropoly acid @ ZIF-8/PAN electrostatic spinning nanofiber precursor
Adding 0.5g of PAN and 0.5g of composite heteropoly acid @ ZIF-8 composite nano particles into 4.5g of DMF solution at the same time, and stirring to form a uniform solution; then, a high-voltage electrostatic spinning machine is utilized to set electrostatic spinning parameter voltage of 20KV, the receiving distance is 20cm, the advancing speed is 0.5ml/H, the diameter of a spinning needle head is 0.6mm, and H is formed by spinning3PW12O40@ ZIF-8/PAN electrospun nanofiber precursor;
(3) finally, carrying out high-temperature carbonization and in-situ phase transformation on the obtained composite heteropoly acid @ ZIF-8/PAN electrostatic spinning nanofiber precursor
Placing the composite heteropoly acid @ ZIF-8/PAN electrostatic spinning nanofiber precursor obtained in the step (2) in a vacuum tube furnace, performing low-temperature pre-oxidation treatment in the air, heating to 800 ℃ at a heating rate of 10 ℃/min under the protection of Ar gas, and introducingActive atmosphere H2And S, preserving the heat for 2 hours to obtain the composite heteropoly acid/polymer electrostatic spinning nanofiber.
Example 13
(1) Firstly, preparing composite heteropoly acid @ ZIF-67 composite nano particles
1.125g of Co (NO)3)2 6H2Cobalt O nitrate was dissolved in 100mL of deionized water, and 1.113g of a heteropoly acid which was H was added thereto3PW12O40And H3PMo12O40After the mixture which is composed according to the mass ratio of 1:1 is uniformly dispersed, 13.75g of 2-methylimidazole is added into the solution, the mixture is stirred and reacted for 24 hours at room temperature, the mixture is centrifuged and washed by deionized water for three times to obtain H3PW12O40@ ZIF-67 composite nano particles are put into a vacuum drying oven to be dried for later use;
(2) then preparing a composite heteropoly acid @ ZIF-67/PAN electrostatic spinning nanofiber precursor
Simultaneously adding 0.5g of PAN and 0.5g of composite heteropoly acid @ ZIF-67 composite nano particles into 4.5g of DMF solution, stirring to form uniform solution, and setting electrostatic spinning parameter voltage of 15KV by using a high-voltage electrostatic spinning machine; the receiving distance is 15 cm; the advancing speed is 0.5 ml/h; the diameter of the spinning needle is 0.6mm, and H is prepared3PW12O40@ ZIF-67/PAN electrospun nanofiber precursor;
(3) finally, carrying out high-temperature carbonization and in-situ phase transformation on the obtained composite heteropoly acid @ ZIF-67/PAN electrostatic spinning nanofiber precursor
Placing the composite heteropoly acid @ ZIF-67/PAN electrostatic spinning nanofiber precursor obtained in the step (2) in a vacuum tube furnace, performing low-temperature pre-oxidation treatment in the air, and then heating at a rate of 10 ℃/min; under the protection of Ar gas, when the temperature is raised to 800 ℃, introducing active atmosphere H2S, preserving the heat for 2h to obtain the POM @ MOFs/polymer electrostatic spinning nanofiber.
Example 14
(1) Firstly, preparing composite heteropoly acid @ ZIF-67 composite nano particles
1.125g of Co (NO)3)2 6H2Cobalt O nitrate was dissolved in 100mL of deionized water, and 1.113g of a heteropoly acid which was H was added thereto3PW12O40And H3PMo12O40After the mixture which is composed according to the mass ratio of 2:1 is uniformly dispersed, 13.75g of 2-methylimidazole is added into the solution, the mixture is stirred and reacted for 24 hours at room temperature, the mixture is centrifuged and washed by deionized water for three times to obtain H3PW12O40@ ZIF-67 composite nano particles are put into a vacuum drying oven to be dried for later use;
(2) then preparing a composite heteropoly acid @ ZIF-67/PAN electrostatic spinning nanofiber precursor
Simultaneously adding 0.5g of PAN and 0.5g of composite heteropoly acid @ ZIF-67 composite nano particles into 4.5g of DMF solution, stirring to form uniform solution, and setting electrostatic spinning parameter voltage of 15KV by using a high-voltage electrostatic spinning machine; the receiving distance is 15 cm; the advancing speed is 0.5 ml/h; the diameter of the spinning needle is 0.6mm, and H is prepared3PW12O40@ ZIF-67/PAN electrospun nanofiber precursor;
(3) finally, carrying out high-temperature carbonization and in-situ phase transformation on the obtained composite heteropoly acid @ ZIF-67/PAN electrostatic spinning nanofiber precursor
Placing the composite heteropoly acid @ ZIF-67/PAN electrostatic spinning nanofiber precursor obtained in the step (2) in a vacuum tube furnace, performing low-temperature pre-oxidation treatment in the air, and then heating at a rate of 10 ℃/min; under the protection of Ar gas, when the temperature is raised to 800 ℃, introducing active atmosphere H2S, preserving the heat for 2h to obtain the POM @ MOFs/polymer electrostatic spinning nanofiber.
Example 15
(1) Firstly, preparing composite heteropoly acid @ ZIF-67 composite nano particles
1.125g of Co (NO)3)2 6H2Cobalt O nitrate was dissolved in 100mL of deionized water, and 1.113g of a heteropoly acid which was H was added thereto3PW12O40And H3PMo12O40After the mixture which is composed according to the mass ratio of 1:2 is uniformly dispersed, 13.75g of 2-methylimidazole is added into the solution, and the mixture is stirred and reacted for 24 hours at room temperatureCentrifuging and rinsing with deionized water for three times to obtain H3PW12O40@ ZIF-67 composite nano particles are put into a vacuum drying oven to be dried for later use;
(2) then preparing a composite heteropoly acid @ ZIF-67/PAN electrostatic spinning nanofiber precursor
Simultaneously adding 0.5g of PAN and 0.5g of composite heteropoly acid @ ZIF-67 composite nano particles into 4.5g of DMF solution, stirring to form uniform solution, and setting electrostatic spinning parameter voltage of 15KV by using a high-voltage electrostatic spinning machine; the receiving distance is 15 cm; the advancing speed is 0.5 ml/h; the diameter of the spinning needle is 0.6mm, and H is prepared3PW12O40@ ZIF-67/PAN electrospun nanofiber precursor;
(3) finally, carrying out high-temperature carbonization and in-situ phase transformation on the obtained composite heteropoly acid @ ZIF-67/PAN electrostatic spinning nanofiber precursor
Placing the composite heteropoly acid @ ZIF-67/PAN electrostatic spinning nanofiber precursor obtained in the step (2) in a vacuum tube furnace, performing low-temperature pre-oxidation treatment in the air, and then heating at a rate of 10 ℃/min; under the protection of Ar gas, when the temperature is raised to 800 ℃, introducing active atmosphere H2S, preserving the heat for 2h to obtain the POM @ MOFs/polymer electrostatic spinning nanofiber.
And (3) performance testing:
the electrocatalytic properties of the POM @ MOFs/polymer electrospun nanofibers obtained in examples 1-15 were tested for ORR/OER performance using a three-electrode test method using an electrochemical workstation and a rotating electrode assembly.
The sample preparation method of the working electrode comprises the following steps:
5mg of catalyst is weighed and dispersed in mixed solution of ethanol/water (volume ratio is 4:1) to prepare catalyst solution, 6 mu L of catalyst solution is dripped on a rotating disk electrode with the diameter of 4mm, and the catalyst solution is naturally dried for standby.
The three-electrode system uses a rotating disc electrode as a working electrode, an Ag/AgCl electrode as a reference electrode and a platinum wire electrode as a counter electrode.
And (3) testing conditions are as follows: introducing oxygen into 0.1M KOH solution for 30min to reach saturation, and performing LSV curve test on ORR performance by using a linear sweep voltammetry curve; the OER performance was tested using an LSV curve in a 1.0M KOH solution using a linear sweep voltammogram.
As shown in FIG. 1, the ORR electrocatalytic effect of the POM @ MOFs/polymer electrospun nanofibers obtained in example 1 is shown, and the linear sweep voltammogram in the graph shows that the initial oxygen reduction potential of the catalyst obtained in example 1 is 0.93V, and the limiting current density at 1600rpm is 5.21mA/cm-2。
As shown in FIG. 2, OER electrocatalytic effect of POM @ MOFs/polymer electrospun nanofibers obtained in example 1 is shown, and the linear sweep voltammogram in the graph shows that the current density of the catalyst obtained in example 1 is 10mAcm-2The corresponding oxygen evolution potential was 1.59V.
In ORR electrocatalysis of POM @ MOFs/polymer electrospun nanofibers obtained in example 2, the initial oxygen reduction potential was 0.94V, and the limiting current density at 1600rpm was 5.15mA/cm-2。
In OER electrocatalysis of POM @ MOFs/polymer electrospun nanofibers obtained in example 2, the current density of the obtained catalyst is 10mAcm-2The corresponding oxygen evolution potential is 1.58V.
In ORR electrocatalysis of POM @ MOFs/Polymer electrospun nanofibers obtained in example 3, the initial oxygen reduction potential was 0.95V, and the limiting current density at 1600rpm was 5.32mA/cm-2。
In OER electrocatalysis of POM @ MOFs/Polymer electrospun nanofibers obtained in example 3, the current density of the obtained catalyst was 10mAcm-2The corresponding oxygen evolution potential was 1.56V.
In ORR electrocatalysis of POM @ MOFs/Polymer electrospun nanofibers obtained in example 4, the initial oxygen reduction potential was 0.91V, and the limiting current density at 1600rpm was 5.21mA/cm-2。
In OER electrocatalysis of POM @ MOFs/Polymer electrospun nanofibers obtained in example 4, the current density of the obtained catalyst was 10mAcm-2The corresponding oxygen evolution potential was 1.54V.
ORR electrocatalysis of POM @ MOFs/Polymer electrospun nanofibers obtained in example 5, with reduction of initial oxygenThe original potential is 0.95V, and the limiting current density at 1600rpm is 5.22mA/cm-2。
In OER electrocatalysis of POM @ MOFs/Polymer electrospun nanofibers obtained in example 5, the catalyst obtained has a current density of 10mAcm-2The corresponding oxygen evolution potential was 1.61V.
In ORR electrocatalysis of POM @ MOFs/Polymer electrospun nanofibers obtained in example 6, the initial oxygen reduction potential was 0.90V, and the limiting current density at 1600rpm was 5.03mA/cm-2。
In OER electrocatalysis of POM @ MOFs/Polymer electrospun nanofibers obtained in example 6, the resulting catalyst current density was 10mAcm-2The corresponding oxygen evolution potential was 1.65V.
In ORR electrocatalysis of POM @ MOFs/Polymer electrospun nanofibers obtained in example 7, the initial oxygen reduction potential was 0.92V, and the limiting current density at 1600rpm was 5.17mA/cm-2。
In OER electrocatalysis of POM @ MOFs/Polymer electrospun nanofibers obtained in example 7, the resulting catalyst current density was 10mAcm-2The corresponding oxygen evolution potential is 1.60V.
In ORR electrocatalysis of POM @ MOFs/Polymer electrospun nanofibers obtained in example 8, the initial oxygen reduction potential was 0.89V, and the limiting current density at 1600rpm was 5.13mA/cm-2。
In OER electrocatalysis of POM @ MOFs/Polymer electrospun nanofibers obtained in example 8, the resulting catalyst current density was 10mAcm-2The corresponding oxygen evolution potential was 1.63V.
In ORR electrocatalysis of POM @ MOFs/Polymer electrospun nanofibers obtained in example 9, the initial oxygen reduction potential was 0.91V, and the limiting current density at 1600rpm was 5.26mA/cm-2。
In OER electrocatalysis of POM @ MOFs/Polymer electrospun nanofibers obtained in example 9, the resulting catalyst current density was 10mAcm-2The corresponding oxygen evolution potential was 1.62V.
ORR electrocatalysis of POM @ MOFs/Polymer electrospun nanofibers obtained in example 10, starting therefromThe oxygen reduction potential was 0.96V and the limiting current density at 1600rpm was 5.36mA/cm-2。
In OER electrocatalysis of POM @ MOFs/Polymer electrospun nanofibers obtained in example 10, the resulting catalyst current density was 10mAcm-2The corresponding oxygen evolution potential was 1.53V.
In ORR electrocatalysis of POM @ MOFs/Polymer electrospun nanofibers obtained in example 11, the initial oxygen reduction potential was 0.97V, and the limiting current density at 1600rpm was 5.47mA/cm-2。
In OER electrocatalysis of POM @ MOFs/Polymer electrospun nanofibers obtained in example 11, the resulting catalyst current density was 10mAcm-2The corresponding oxygen evolution potential is 1.50V.
In ORR electrocatalysis of POM @ MOFs/Polymer electrospun nanofibers obtained in example 12, the initial oxygen reduction potential was 0.98V, and the limiting current density at 1600rpm was 5.56mA/cm-2。
In OER electrocatalysis of POM @ MOFs/Polymer electrospun nanofibers obtained in example 12, the resulting catalyst current density was 10mAcm-2The corresponding oxygen evolution potential was 1.47V.
In ORR electrocatalysis of POM @ MOFs/Polymer electrospun nanofibers obtained in example 13, the initial oxygen reduction potential was 0.96V, and the limiting current density at 1600rpm was 5.34mA/cm-2。
OER electrocatalysis of POM @ MOFs/Polymer electrospun nanofibers obtained in example 13, resulting in a catalyst current density of 10mAcm-2The corresponding oxygen evolution potential was 1.54V.
In ORR electrocatalysis of POM @ MOFs/Polymer electrospun nanofibers obtained in example 14, the initial oxygen reduction potential was 0.99V, and the limiting current density at 1600rpm was 5.63mA/cm-2。
OER electrocatalysis of POM @ MOFs/Polymer electrospun nanofibers obtained in example 14, resulting in a catalyst current density of 10mAcm-2The corresponding oxygen evolution potential is 1.46V.
ORR electrocatalysis of POM @ MOFs/Polymer electrospun nanofibers obtained in example 15Wherein the initial oxygen reduction potential is 0.97V and the limiting current density at 1600rpm is 5.52mA/cm-2。
In OER electrocatalysis of POM @ MOFs/Polymer electrospun nanofibers obtained in example 15, the resulting catalyst current density was 10mAcm-2The corresponding oxygen evolution potential is 1.50V.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.

Claims (9)

1. The heteropoly acid @ MOFs/polymer electrostatic spinning nanofiber is characterized by being prepared according to the following steps:
(1) POM is encapsulated in a MOFs material hole limited range, and POM @ MOFs composite nanoparticles are obtained;
(2) loading the POM @ MOFs composite nanoparticles in the polymer nanofiber by using an electrostatic spinning technology to obtain a POM @ MOFs/polymer nanofiber precursor;
(3) and controlling a carbonization mode, and realizing in-situ doping of transition metal and hetero atoms on the POM @ MOFs/polymer nanofiber precursor to obtain the heteropoly acid @ MOFs/polymer electrostatic spinning nanofiber.
2. The heteropoly acid @ MOFs/polymer electrospun nanofiber according to claim 1, wherein said MOFs material is ZIF-8 or ZIF-67.
3. The heteropoly acid @ MOFs/polymer electrospun nanofibers according to claim 1, wherein said POM is H3PMo12O40、H3PW12O40And mixtures thereof.
4. The heteropoly acid @ MOFs/polymer electrospun nanofibers according to claim 1, wherein said polymer is PAN, PVA, PVP or PS.
5. The heteropoly acid @ MOFs/polymer electrospun nanofibers according to claim 1, wherein said step (1) is specifically performed according to the following steps:
the preparation method comprises the steps of taking a small-molecule organic ligand, soluble metal salt and heteropoly acid as initial raw materials, and adopting a solvothermal method to realize the confinement encapsulation of POM in MOFs pores to prepare the POM @ MOFs composite nanoparticles.
6. The heteropoly acid @ MOFs/polymer electrospun nanofibers according to claim 1, wherein said step (2) is specifically performed according to the following steps:
the POM @ MOFs/polymer composite nanofiber precursor is obtained by taking a high-molecular polymer, POM @ MOFs composite nanoparticles and an organic solvent as initial raw materials and adopting a coaxial electrostatic spinning technology.
7. The heteropoly acid @ MOFs/polymer electrospun nanofibers according to claim 6, characterized in that said electrospinning technique has the process parameters: electrostatic spinning voltage is 15-20 KV; the receiving distance is 15-20 cm; the advancing speed is 0.5ml/h, and the diameter of the spinning needle is 0.6 mm.
8. The heteropoly acid @ MOFs/polymer electrospun nanofibers according to claim 1, wherein said step (3) is specifically performed according to the following steps:
placing the POM @ MOFs/polymer nanofiber precursor in a vacuum tube furnace, firstly carrying out low-temperature pre-oxidation treatment in the air, then raising the temperature to 800 ℃ under the protection of Ar gas, and introducing an active atmosphere (H)2，H2O，H2S), preserving heat for 2h, and realizing synchronous high-temperature carbonization and in-situ phase conversion to obtain the heteropoly acid @ MOFs/polymer electrostatic spinning nanofiber.
9. The heteropoly acid @ MOFs/polymer electrospun nanofibers according to claim 8, wherein said low temperature pre-oxidation treatment is a 2 ℃/min ramp to 280 ℃/min in air atmosphere and hold for 2 h.
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Citations (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080128941A1 (en) * 2006-11-14 2008-06-05 Miguel Angel Caballero Lopez Process for the additivation of synthetic fibres, artificial fibres and polymers with special properties
CN103191786A (en) * 2013-04-23 2013-07-10 浙江师范大学 Preparation method of MIL-100(Fe) packaged phosphotungstic heteropolyacid catalyst
CN108114749A (en) * 2016-11-29 2018-06-05 中国石油化工股份有限公司 A kind of heteropolyacid catalyst and preparation method thereof
CN108736031A (en) * 2018-05-21 2018-11-02 同济大学 A kind of self-supporting PtCo alloy nanoparticle catalyst and the preparation method and application thereof
CN110052282A (en) * 2019-05-05 2019-07-26 西北师范大学 A kind of preparation and application of transition metal phosphide/hud typed nitrogen-doped carbon nano-fiber composite material
CN110404555A (en) * 2019-08-09 2019-11-05 温州大学 A kind of preparation method of mesoporous carbon coating cobalt platinum intermetallic compound catalyst
CN110504458A (en) * 2019-07-05 2019-11-26 江苏大学 A kind of preparation method of bimetallic-nitrogen-doped carbon nano electro-catalytic material
WO2020016067A1 (en) * 2018-07-16 2020-01-23 Freie Universität Berlin Atomic metal- and n-doped open-mesoporous carbon nanofibers for efficient and bio-adaptable oxygen electrode in metal-air batteries
CN110783582A (en) * 2019-11-06 2020-02-11 浙江理工大学 Nitrogen-doped carbon nanotube-loaded nitrogen-doped carbon-coated iron-cobalt alloy dual-function catalyst and preparation method and application thereof
CN111013606A (en) * 2019-12-27 2020-04-17 江南大学 Homogeneous AuNi alloy catalytic material and preparation method thereof
CN111081995A (en) * 2019-11-07 2020-04-28 东北大学 Preparation method of metal oxide carbon nanofiber electrode material based on MOFs derivation
CN111068734A (en) * 2019-12-24 2020-04-28 新疆大学 Bamboo-like nitrogen-doped carbon nanofiber-coated transition metal alloy nanoparticle catalytic material for efficient bifunctional electrocatalysis
CN111602213A (en) * 2018-01-17 2020-08-28 同和电子科技有限公司 Fe-Co alloy powder, and molded body for inductor and inductor using same
US20200406248A1 (en) * 2019-06-26 2020-12-31 Xergy Inc. Anionic membranes incorporating functional additives
AU2020103787A4 (en) * 2020-11-30 2021-02-11 Junada (qingdao) Technology Co., Ltd. SiO2/PVDF-HFP Composite Fiber Membrane and Its Preparation Method and Application
CN112517077A (en) * 2020-12-09 2021-03-19 三峡大学 Preparation method and application of heteropolyacid-doped ZIF-67 catalyst
CN112725819A (en) * 2021-01-20 2021-04-30 新疆大学 Tungsten-molybdenum-based nitrogen carbide nano material and preparation method and application thereof
CN112928287A (en) * 2021-03-11 2021-06-08 济南易航新材料科技有限公司 N, P double-doped carbon fiber loaded CoP composite catalytic material and preparation method and application thereof
CN113198541A (en) * 2021-05-19 2021-08-03 北京单原子催化科技有限公司 MOFs @ M1Single atom site catalyst of polyacid, preparation and application
CN113540478A (en) * 2021-07-12 2021-10-22 南京工业大学 Porous carbon-based nanofiber film material loaded by metal single atom and metal derivative thereof, and preparation method and application thereof
CN113559725A (en) * 2021-08-27 2021-10-29 深圳市爱玛特科技有限公司 Preparation method of metal organic framework polyamide thin-layer nano composite membrane (UiO-66/TFN)
CN113652706A (en) * 2021-06-28 2021-11-16 深圳大学 Composite electrocatalyst and preparation method and application thereof

Patent Citations (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080128941A1 (en) * 2006-11-14 2008-06-05 Miguel Angel Caballero Lopez Process for the additivation of synthetic fibres, artificial fibres and polymers with special properties
CN103191786A (en) * 2013-04-23 2013-07-10 浙江师范大学 Preparation method of MIL-100(Fe) packaged phosphotungstic heteropolyacid catalyst
CN108114749A (en) * 2016-11-29 2018-06-05 中国石油化工股份有限公司 A kind of heteropolyacid catalyst and preparation method thereof
CN111602213A (en) * 2018-01-17 2020-08-28 同和电子科技有限公司 Fe-Co alloy powder, and molded body for inductor and inductor using same
CN108736031A (en) * 2018-05-21 2018-11-02 同济大学 A kind of self-supporting PtCo alloy nanoparticle catalyst and the preparation method and application thereof
WO2020016067A1 (en) * 2018-07-16 2020-01-23 Freie Universität Berlin Atomic metal- and n-doped open-mesoporous carbon nanofibers for efficient and bio-adaptable oxygen electrode in metal-air batteries
CN110052282A (en) * 2019-05-05 2019-07-26 西北师范大学 A kind of preparation and application of transition metal phosphide/hud typed nitrogen-doped carbon nano-fiber composite material
US20200406248A1 (en) * 2019-06-26 2020-12-31 Xergy Inc. Anionic membranes incorporating functional additives
CN110504458A (en) * 2019-07-05 2019-11-26 江苏大学 A kind of preparation method of bimetallic-nitrogen-doped carbon nano electro-catalytic material
CN110404555A (en) * 2019-08-09 2019-11-05 温州大学 A kind of preparation method of mesoporous carbon coating cobalt platinum intermetallic compound catalyst
CN110783582A (en) * 2019-11-06 2020-02-11 浙江理工大学 Nitrogen-doped carbon nanotube-loaded nitrogen-doped carbon-coated iron-cobalt alloy dual-function catalyst and preparation method and application thereof
CN111081995A (en) * 2019-11-07 2020-04-28 东北大学 Preparation method of metal oxide carbon nanofiber electrode material based on MOFs derivation
CN111068734A (en) * 2019-12-24 2020-04-28 新疆大学 Bamboo-like nitrogen-doped carbon nanofiber-coated transition metal alloy nanoparticle catalytic material for efficient bifunctional electrocatalysis
CN111013606A (en) * 2019-12-27 2020-04-17 江南大学 Homogeneous AuNi alloy catalytic material and preparation method thereof
AU2020103787A4 (en) * 2020-11-30 2021-02-11 Junada (qingdao) Technology Co., Ltd. SiO2/PVDF-HFP Composite Fiber Membrane and Its Preparation Method and Application
CN112517077A (en) * 2020-12-09 2021-03-19 三峡大学 Preparation method and application of heteropolyacid-doped ZIF-67 catalyst
CN112725819A (en) * 2021-01-20 2021-04-30 新疆大学 Tungsten-molybdenum-based nitrogen carbide nano material and preparation method and application thereof
CN112928287A (en) * 2021-03-11 2021-06-08 济南易航新材料科技有限公司 N, P double-doped carbon fiber loaded CoP composite catalytic material and preparation method and application thereof
CN113198541A (en) * 2021-05-19 2021-08-03 北京单原子催化科技有限公司 MOFs @ M1Single atom site catalyst of polyacid, preparation and application
CN113652706A (en) * 2021-06-28 2021-11-16 深圳大学 Composite electrocatalyst and preparation method and application thereof
CN113540478A (en) * 2021-07-12 2021-10-22 南京工业大学 Porous carbon-based nanofiber film material loaded by metal single atom and metal derivative thereof, and preparation method and application thereof
CN113559725A (en) * 2021-08-27 2021-10-29 深圳市爱玛特科技有限公司 Preparation method of metal organic framework polyamide thin-layer nano composite membrane (UiO-66/TFN)

Non-Patent Citations (11)

* Cited by examiner, † Cited by third party
Title
JIAN-WEI DING等: "A new green system of HPW@MOFs catalyzed desulfurization using O_2 as oxidant", 《CHINESE CHEMICAL LETTERS》, no. 05, 15 May 2016 (2016-05-15) *
余祖熙等: "《化肥催化剂使用技术》", 化学工业出版社 *
余祖熙等: "《化肥催化剂使用技术》", 化学工业出版社, pages: 724 *
先兆伟等: "多酸基纳米复合材料的制备及性能研究进展", 《江汉大学学报(自然科学版)》 *
先兆伟等: "多酸基纳米复合材料的制备及性能研究进展", 《江汉大学学报(自然科学版)》, no. 02, 28 April 2015 (2015-04-28) *
刘江涛等: "镍铁合金纳米颗粒嵌入氮掺杂碳纳米纤维高活性析氧催化剂的研究", 《现代化工》 *
刘江涛等: "镍铁合金纳米颗粒嵌入氮掺杂碳纳米纤维高活性析氧催化剂的研究", 《现代化工》, no. 12, 20 December 2019 (2019-12-20) *
周颖等: "纳米多相催化材料在常温反应中的应用", 《化工进展》 *
周颖等: "纳米多相催化材料在常温反应中的应用", 《化工进展》, no. 10, 5 October 2015 (2015-10-05) *
钟佳: ""静电纺丝法制备一维钴基碳纤维及其氧还原性能研究"", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 *
钟佳: ""静电纺丝法制备一维钴基碳纤维及其氧还原性能研究"", 《中国优秀硕士学位论文全文数据库 工程科技I辑》, no. 2020, 15 February 2020 (2020-02-15), pages 29 - 32 *

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