CN114400339B - heteropolyacid@MOFs/polymer electrostatic spinning nanofiber - Google Patents

heteropolyacid@MOFs/polymer electrostatic spinning nanofiber Download PDF

Info

Publication number
CN114400339B
CN114400339B CN202111476549.4A CN202111476549A CN114400339B CN 114400339 B CN114400339 B CN 114400339B CN 202111476549 A CN202111476549 A CN 202111476549A CN 114400339 B CN114400339 B CN 114400339B
Authority
CN
China
Prior art keywords
zif
heteropolyacid
composite
mofs
electrostatic spinning
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202111476549.4A
Other languages
Chinese (zh)
Other versions
CN114400339A (en
Inventor
牛其建
王涛
陆宇豪
王雪婧
王承建
董秀秀
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangsu University
Original Assignee
Jiangsu University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jiangsu University filed Critical Jiangsu University
Priority to CN202111476549.4A priority Critical patent/CN114400339B/en
Publication of CN114400339A publication Critical patent/CN114400339A/en
Application granted granted Critical
Publication of CN114400339B publication Critical patent/CN114400339B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9008—Organic or organo-metallic compounds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/054—Electrodes comprising electrocatalysts supported on a carrier
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
    • C25B11/056—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of textile or non-woven fabric
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
    • C25B11/069—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of at least one single element and at least one compound; consisting of two or more compounds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9041—Metals or alloys

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Nonwoven Fabrics (AREA)
  • Artificial Filaments (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)

Abstract

The invention relates to the technical field of electrochemical catalysis, in particular to heteropolyacid@MOFs/polymer electrostatic spinning nanofiber. MOFs are easy to cause structural collapse in the carbonization process, so that active particles are seriously agglomerated, and the full play of the electrocatalytic performance of the catalyst is limited. Based on the problems, the invention provides a heteropolyacid@MOFs/polymer electrostatic spinning nanofiber, which encapsulates transition metal and hetero atoms by adopting double domain limiting effect of MOFs materials and high polymer electrostatic spinning fibers, reduces aggregation phenomenon among nanoparticles, improves distribution condition of metal nanoparticles in a catalyst material, and fully plays electrocatalytic performance of the obtained composite catalyst.

Description

heteropolyacid@MOFs/polymer electrostatic spinning nanofiber
Technical Field
The invention relates to the technical field of electrochemical catalysis, in particular to heteropolyacid@MOFs/polymer electrostatic spinning nanofiber.
Background
Oxygen reduction and oxygen evolution reactions (ORR/OER) are the core reactions of many new energy conversion and storage devices (fuel cells, metal-air cells and water electrolysis devices). However, these two types of reactions are slow in kinetics and need to be catalyzed to proceed efficiently.
The ORR/OER dual-function catalyst mainly comprises: noble metal catalysts, transition metal catalysts, carbon material catalysts, and composite material catalysts thereof. Noble metal catalysts are costly and poorly stable for large-scale commercial applications. Transition metal catalysts are limited by poor electrical conductivity and often require the incorporation of electron donors (metal nanoparticles) or conductive materials (carbon or metal support materials). In addition, heteroatom (N, P, S) -doped carbon materials are of great interest because of their high conductivity, porous structure, high thermal and chemical stability, and the like. The transition metal catalyst is compounded with the carbon material, and the development of a novel high-efficiency electrocatalyst has become a research hot spot.
However, combining transition metal catalysts with heteroatom doped carbon materials, preparing ORR/OER dual function catalysts with porous structures and high active components by simple processes remains a challenge. Because accurate regulation and control on the composition, structure and size of the precursor cannot be realized, insufficient and uneven exposure of the catalytic active sites are easily caused, and the characteristics of the metal-organic framework polymers (MOFs) with adjustable morphology, composition and structure are proved to be a novel precursor for preparing the transition metal/heteroatom doped porous carbon material composite catalyst. However, MOFs are prone to structural collapse during carbonization, which results in serious agglomeration of active particles, and limit full play of the electrocatalytic performance of the catalyst.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to solve the technical problems that: MOFs are easy to cause structural collapse in the carbonization process, so that active particles are seriously agglomerated, and the full play of the electrocatalytic performance of the catalyst is limited.
The technical scheme adopted for solving the technical problems is as follows: the invention provides heteropoly acid@MOFs/polymer electrostatic spinning nanofiber which is prepared according to the following steps:
(1) Encapsulating heteropolyacid (POM) by adopting MOFs material pores in a limited domain manner to obtain POM@MOFs composite nano particles;
(2) The electrostatic spinning technology is utilized to realize that POM@MOFs composite nano particles are loaded in the polymer nano fiber to obtain a POM@MOFs/polymer nano fiber precursor;
(3) And (3) 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 heteropolyacid@MOFs/polymer electrospun nanofiber.
Specifically, the MOFs material is ZIF-8 or ZIF-67.
Specifically, the POM is H 3 PMo 12 O 40 、H 3 PW 12 O 40 And mixtures thereof.
In particular, the polymer is PAN, PVA, PVP or PS.
Specifically, the step (1) is specifically performed according to the following steps:
the POM@MOFs composite nano particle is prepared by taking a small molecular organic ligand, a soluble metal salt and heteropolyacid as initial raw materials and adopting a solvothermal method to realize the domain-limited encapsulation of POM in MOFs holes.
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 nano particles and an organic solvent as initial raw materials through a coaxial electrostatic spinning technology.
Specifically, the electrostatic spinning technology comprises the following technological parameters: electrostatic spinning voltage is 15-20KV; the receiving distance is 15cm to 20cm; the advancing speed is 0.5ml/h, and the diameter of the spinning needle is 0.6mm.
Specifically, the step (3) is specifically performed according to the following steps:
placing POM@MOFs/polymer nanofiber precursor in a vacuum tube furnace, pre-oxidizing in air at low temperature, heating to target carbonization temperature of 800 ℃ under Ar protection, and introducing active atmosphere (H) 2 、H 2 O or H 2 S), preserving heat for 2h, and realizing synchronous high-temperature carbonization and in-situ phase transformation to obtain the heteropoly acid@MOFs/polymer electrostatic spinning nanofiber.
Specifically, the low-temperature pre-oxidation treatment is to heat up to 280 ℃ per minute at a speed of 2 ℃ per minute in an air atmosphere and keep the temperature for 2 hours.
The beneficial effects of the invention are as follows:
the invention provides a heteropolyacid@MOFs/polymer electrostatic spinning nanofiber, which adopts double-domain-limited effect of MOFs material and high polymer electrostatic spinning fiber to encapsulate transition metal and hetero atoms, reduces agglomeration phenomenon among nano particles, improves distribution condition of metal nano particles in a catalyst material, provides a high-conductivity electron transmission channel, and can fully play the electrocatalytic performance of the obtained composite catalyst.
Drawings
Fig. 1: ORR electrocatalytic properties of the pom@mofs/polymer electrospun nanofibers obtained in example 1.
Fig. 2: OER electrocatalytic properties of the pom@mofs/polymer electrospun nanofibers obtained in example 1.
Detailed Description
The invention will now be described in further detail with reference to the accompanying drawings.
The low temperature pre-oxidation treatment in the following examples of the present invention was performed by heating to 280 c/min at a rate of 2 c/min in an air atmosphere and maintaining the temperature for 2 hours.
Example 1
(1) First, H is prepared 3 PW 12 O 40 Composite ZIF-8 nanoparticle
1.125g Zn (NO) 3 ) 2 6H 2 Zinc O nitrate was dissolved in 100mL of deionized water, to which was then added 1.113g H 3 PW 12 O 40 After the mixture is uniformly dispersed, 13.75g of 2-methylimidazole is added into the solution, stirred at room temperature for reaction for 24 hours, centrifuged and washed three times by deionized water, thus obtaining H 3 PW 12 O 40 The @ ZIF-8 composite nano particles are put into a vacuum drying oven for drying for standby;
(2) Followed by preparation of H 3 PW 12 O 40 Nano fiber precursor for @ ZIF-8/PAN electrostatic spinning
0.5g of PAN and 0.5g ofg H 3 PW 12 O 40 Adding the @ 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 used for setting electrostatic spinning parameter voltage of 20KV, receiving distance of 20cm, advancing speed of 0.5ml/H, diameter of a spinning needle head of 0.6mm, and spinning is carried out to form H 3 PW 12 O 40 @ ZIF-8/PAN electrospun nanofiber precursor;
(3) Finally, for the obtained H 3 PW 12 O 40 High-temperature carbonization and in-situ phase transformation of ZIF-8/PAN electrospun nanofiber precursor
H obtained in the step (2) 3 PW 12 O 40 Placing ZIF-8/PAN electrospun nanofiber precursor in a vacuum tube furnace, pre-oxidizing in air at low temperature, heating at 10deg.C/min, heating to 800deg.C under Ar gas, and introducing active atmosphere H 2 S, preserving heat for 2 hours to obtain the POM@MOFs/polymer electrostatic spinning nanofiber.
Example 2
(1) First, H is prepared 3 PMo 12 O 40 Composite ZIF-8 nanoparticle
1.125g Zn (NO) 3 ) 2 6H 2 Zinc O nitrate was dissolved in 100mL of deionized water, to which was then added 1.113g H 3 PMo 12 O 40 After the mixture is uniformly dispersed, 13.75g of 2-methylimidazole is added into the solution, stirred at room temperature for reaction for 24 hours, centrifuged and washed three times by deionized water to obtain H 3 PMo 12 O 40 Putting the composite nano particles @ ZIF-8 into a vacuum drying oven, and drying for later use;
(2) Followed by preparation of H 3 PMo 12 O 40 Nano fiber precursor for @ ZIF-8/PAN electrostatic spinning
0.5g of PAN and 0.5. 0.5g H 3 PMo 12 O 40 Adding the @ ZIF-8 composite nano particles into 4.5g of DMF solution at the same time, stirring to form a uniform solution, and then setting electrostatic spinning parameter voltage to 20KV by using a high-voltage electrostatic spinning machine; a receiving distance of 20cm; the propulsion rate is 0.5ml/h; the diameter of the spinning needle is 0.6mm, and H is formed by preparation 3 PMo 12 O 40 @ ZIF-8/PAN electrospun nanofiber precursor;
(3) Finally, for the obtained H 3 PMo 12 O 40 High temperature carbonization and in situ phase transformation (active atmosphere H) of the precursor ZIF-8/PAN electrospun nanofiber 2 S)
H obtained in the step (2) 3 PMo 12 O 40 Placing ZIF-8/PAN electrospun nanofiber precursor in a vacuum tube furnace, pre-oxidizing in air at low temperature, heating at 10deg.C/min, heating to 800deg.C under Ar gas, and introducing active atmosphere H 2 S, preserving heat for 2 hours to obtain the POM@MOFs/polymer electrostatic spinning nanofiber.
Example 3
(1) First, H is prepared 3 PW 12 O 40 Composite nano particle @ ZIF-67
1.125g Co (NO) 3 ) 2 6H 2 Cobalt nitrate O was dissolved in 100mL of deionized water, to which was then added 1.113g H 3 PW 12 O 40 After the mixture is uniformly dispersed, 13.75g of 2-methylimidazole is added into the solution, stirred at room temperature for reaction for 24 hours, centrifuged and washed three times by deionized water to obtain H 3 PW 12 O 40 Putting the @ ZIF-67 composite nano particles into a vacuum drying oven for drying for later use;
(2) Followed by preparation of H 3 PW 12 O 40 Nano fiber precursor for @ ZIF-67/PAN electrostatic spinning
0.5g of PAN and 0.5. 0.5g H 3 PW 12 O 40 Adding the @ ZIF-67 composite nano particles into 4.5g of DMF solution at the same time, stirring to form a uniform solution, and then setting electrostatic spinning parameter voltage to 15KV by using a high-voltage electrostatic spinning machine; the receiving distance is 15cm; the propulsion rate is 0.5ml/h; the diameter of the spinning needle is 0.6mm, and H is formed by preparation 3 PW 12 O 40 @ ZIF-67/PAN electrospun nanofiber precursor;
(3) Finally, for the obtained H 3 PW 12 O 40 High-temperature carbonization and in-situ phase transformation of @ ZIF-67/PAN electrospun nanofiber precursor
H obtained in the step (2) 3 PW 12 O 40 Placing the @ ZIF-67/PAN electrospun nanofiber precursor in a vacuum tube furnace, performing low-temperature pre-oxidation treatment in air, and then performing heating at a speed of 10 ℃/min; under the protection of Ar gas, when the temperature is raised to 800 ℃, the active atmosphere H is introduced 2 S, preserving heat for 2 hours to obtain the POM@MOFs/polymer electrostatic spinning nanofiber.
Example 4
(1) First, H is prepared 3 PMo 12 O 40 Composite nano particle @ ZIF-67
1.125g Co (NO) 3 ) 2 6H 2 Cobalt nitrate O was dissolved in 100mL of deionized water, to which was then added 1.113g H 3 PMo 12 O 40 After the mixture is uniformly dispersed, 13.75g of 2-methylimidazole is added into the solution, stirred at room temperature for reaction for 24 hours, centrifuged and washed three times by deionized water to obtain H 3 PMo 12 O 40 Putting the @ ZIF-67 composite nano particles into a vacuum drying oven, and drying for later use;
(2) Followed by preparation of H 3 PMo 12 O 40 Nano fiber precursor for @ ZIF-67/PAN electrostatic spinning
0.5g of PAN and 0.5. 0.5g H 3 PMo 12 O 40 Adding the @ ZIF-67 composite nano particles into 4.5g of DMF solution at the same time, stirring to form a uniform solution, and then setting electrostatic spinning parameter voltage to 20KV by using a high-voltage electrostatic spinning machine; a receiving distance of 20cm; the propulsion rate is 0.5ml/h; the diameter of the spinning needle is 0.6mm, and H is formed by preparation 3 PMo 12 O 40 @ ZIF-67/PAN electrospun nanofiber precursor;
(3) Finally, for the obtained H 3 PMo 12 O 40 High-temperature carbonization and in-situ phase transformation of @ ZIF-67/PAN electrospun nanofiber precursor
H obtained in the step (2) 3 PMo 12 O 40 Placing the @ ZIF-67/PAN electrospun nanofiber precursor in a vacuum tube furnace, performing low-temperature pre-oxidation treatment in air, and then heating at a heating rate of 10 ℃/min; under the protection of Ar gas, when the temperature is raised to 800 ℃, the living air is introducedAtmosphere H 2 S, preserving heat for 2h; thus obtaining POM@MOFs/polymer electrostatic spinning nanofiber.
Example 5
(1) First, H is prepared 3 PW 12 O 40 Composite ZIF-8 nanoparticle
1.125g Zn (NO) 3 ) 2 6H 2 Zinc O nitrate was dissolved in 100mL of deionized water, to which was then added 1.113g H 3 PW 12 O 40 After the mixture is uniformly dispersed, 13.75g of 2-methylimidazole is added into the solution, stirred at room temperature for reaction for 24 hours, centrifuged and washed three times by deionized water, thus obtaining H 3 PW 12 O 40 The @ ZIF-8 composite nano particles are put into a vacuum drying oven for drying for standby;
(2) Followed by preparation of H 3 PW 12 O 40 Nano fiber precursor for @ ZIF-8/PAN electrostatic spinning
0.5g of PAN and 0.5. 0.5g H 3 PW 12 O 40 Adding the @ 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 used for setting electrostatic spinning parameter voltage of 20KV, receiving distance of 20cm, advancing speed of 0.5ml/H, diameter of a spinning needle head of 0.6mm, and spinning is carried out to form H 3 PW 12 O 40 @ ZIF-8/PAN electrospun nanofiber precursor;
(3) Finally, for the obtained H 3 PW 12 O 40 High-temperature carbonization and in-situ phase transformation of ZIF-8/PAN electrospun nanofiber precursor
H obtained in the step (2) 3 PW 12 O 40 Placing ZIF-8/PAN electrospun nanofiber precursor in a vacuum tube furnace, pre-oxidizing in air at low temperature, heating at 10deg.C/min, heating to 800deg.C under Ar gas, and introducing active atmosphere H 2 And (3) preserving heat for 2 hours to obtain the POM@MOFs/polymer electrostatic spinning nanofiber.
Example 6
(1) First, H is prepared 3 PW 12 O 40 Composite ZIF-8 nanoparticle
1.125g Zn (NO) 3 ) 2 6H 2 Zinc O nitrate was dissolved in 100mL of deionized water, to which was then added 1.113g H 3 PW 12 O 40 After the mixture is uniformly dispersed, 13.75g of 2-methylimidazole is added into the solution, stirred at room temperature for reaction for 24 hours, centrifuged and washed three times by deionized water, thus obtaining H 3 PW 12 O 40 The @ ZIF-8 composite nano particles are put into a vacuum drying oven for drying for standby;
(2) Followed by preparation of H 3 PW 12 O 40 Nano fiber precursor for @ ZIF-8/PAN electrostatic spinning
0.5g of PAN and 0.5. 0.5g H 3 PW 12 O 40 Adding the @ 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 used for setting electrostatic spinning parameter voltage of 20KV, receiving distance of 20cm, advancing speed of 0.5ml/H, diameter of a spinning needle head of 0.6mm, and spinning is carried out to form H 3 PW 12 O 40 @ ZIF-8/PAN electrospun nanofiber precursor;
(3) Finally, for the obtained H 3 PW 12 O 40 High-temperature carbonization and in-situ phase transformation of ZIF-8/PAN electrospun nanofiber precursor
H obtained in the step (2) 3 PW 12 O 40 Placing ZIF-8/PAN electrospun nanofiber precursor in a vacuum tube furnace, pre-oxidizing in air at low temperature, heating at 10deg.C/min, heating to 800deg.C under Ar gas, and introducing active atmosphere H 2 O, preserving heat for 2h to obtain the POM@MOFs/polymer electrostatic spinning nanofiber.
Example 7
(1) First, H is prepared 3 PW 12 O 40 Composite ZIF-8 nanoparticle
1.125g Zn (NO) 3 ) 2 6H 2 Zinc O nitrate was dissolved in 100mL of deionized water, to which was then added 1.113g H 3 PW 12 O 40 After it was uniformly dispersed, 13.75g of 2-methylimidazole was added to the solution, stirred at room temperature for 24 hours, centrifuged and rinsed with deionized waterThree times to obtain H 3 PW 12 O 40 The @ ZIF-8 composite nano particles are put into a vacuum drying oven for drying for standby;
(2) Followed by preparation of H 3 PW 12 O 40 Nano fiber precursor for @ ZIF-8/PVA electrostatic spinning
0.5g PVA and 0.5. 0.5g H 3 PW 12 O 40 Adding the @ 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 used for setting electrostatic spinning parameter voltage of 20KV, receiving distance of 20cm, advancing speed of 0.5ml/H, diameter of a spinning needle head of 0.6mm, and spinning is carried out to form H 3 PW 12 O 40 @ ZIF-8/PAN electrospun nanofiber precursor;
(3) Finally, for the obtained H 3 PW 12 O 40 High-temperature carbonization and in-situ phase transformation are carried out on ZIF-8/PVA electrospun nanofiber precursor
H obtained in the step (2) 3 PW 12 O 40 Placing ZIF-8/PVA electrostatic spinning nanofiber precursor in a vacuum tube furnace, pre-oxidizing in air at low temperature, heating at 10deg.C/min, heating to 800deg.C under Ar gas protection, and introducing active atmosphere H 2 S, preserving heat for 2 hours to obtain the POM@MOFs/polymer electrostatic spinning nanofiber.
Example 8
(1) First, H is prepared 3 PW 12 O 40 Composite ZIF-8 nanoparticle
1.125g Zn (NO) 3 ) 2 6H 2 Zinc O nitrate was dissolved in 100mL of deionized water, to which was then added 1.113g H 3 PW 12 O 40 After the mixture is uniformly dispersed, 13.75g of 2-methylimidazole is added into the solution, stirred at room temperature for reaction for 24 hours, centrifuged and washed three times by deionized water, thus obtaining H 3 PW 12 O 40 The @ ZIF-8 composite nano particles are put into a vacuum drying oven for drying for standby;
(2) Followed by preparation of H 3 PW 12 O 40 @ ZIF-8/PVP electrospun nanofiber precursor
0.5g PVP and 0.5. 0.5g H 3 PW 12 O 40 Adding the @ 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 used for setting electrostatic spinning parameter voltage of 20KV, receiving distance of 20cm, advancing speed of 0.5ml/H, diameter of a spinning needle head of 0.6mm, and spinning is carried out to form H 3 PW 12 O 40 @ ZIF-8/PVP electrospun nanofiber precursor;
(3) Finally, for the obtained H 3 PW 12 O 40 High-temperature carbonization and in-situ phase transformation of ZIF-8/PVP electrospun nanofiber precursor
H obtained in the step (2) 3 PW 12 O 40 Placing ZIF-8/PVP electrostatic spinning nanofiber precursor in a vacuum tube furnace, pre-oxidizing in air at low temperature, heating at 10deg.C/min, heating to 800deg.C under Ar gas protection, and introducing active atmosphere H 2 S, preserving heat for 2 hours to obtain the POM@MOFs/polymer electrostatic spinning nanofiber.
Example 9
(1) First, H is prepared 3 PW 12 O 40 Composite ZIF-8 nanoparticle
1.125g Zn (NO) 3 ) 2 6H 2 Zinc O nitrate was dissolved in 100mL of deionized water, to which was then added 1.113g H 3 PW 12 O 40 After the mixture is uniformly dispersed, 13.75g of 2-methylimidazole is added into the solution, stirred at room temperature for reaction for 24 hours, centrifuged and washed three times by deionized water, thus obtaining H 3 PW 12 O 40 The @ ZIF-8 composite nano particles are put into a vacuum drying oven for drying for standby;
(2) Followed by preparation of H 3 PW 12 O 40 @ ZIF-8/PS electrospun nanofiber precursor
0.5g PS and 0.5. 0.5g H 3 PW 12 O 40 Adding the @ 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 used for setting electrostatic spinning parameter voltage to 20KV, receiving distance to 20cm and advancing speed to 0.5ml/h, and diameter of a spinning needle head is set0.6mm, spun to form H 3 PW 12 O 40 @ ZIF-8/PS electrospun nanofiber precursor;
(3) Finally, for the obtained H 3 PW 12 O 40 High-temperature carbonization and in-situ phase transformation are carried out on ZIF-8/PS electrospun nanofiber precursor
H obtained in the step (2) 3 PW 12 O 40 Placing ZIF-8/PS electrospun nanofiber precursor in a vacuum tube furnace, pre-oxidizing in air at low temperature, heating at 10deg.C/min, heating to 800deg.C under Ar gas, and introducing active atmosphere H 2 S, preserving heat for 2 hours to obtain the POM@MOFs/polymer electrostatic spinning nanofiber.
Example 10
(1) Firstly, preparing composite heteropolyacid@ZIF-8 composite nano particles
1.125g Zn (NO) 3 ) 2 6H 2 Zinc O nitrate was dissolved in 100mL of deionized water, to which was then added 1.113g of a heteropolyacid H 3 PW 12 O 40 And H is 3 PMo 12 O 40 Adding 13.75g of 2-methylimidazole into the solution after the mixture is uniformly dispersed according to the mass ratio of 1:1, stirring at room temperature for reaction for 24 hours, centrifuging and flushing with deionized water for three times to obtain composite heteropolyacid@ZIF-8 composite nano particles, and putting the composite nano particles into a vacuum drying oven for drying for later use;
(2) Then preparing the composite heteropolyacid@ZIF-8/PAN electrospun 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 simultaneously, and stirring to form a uniform solution; then, a high-voltage electrostatic spinning machine is used for setting electrostatic spinning parameter voltage of 20KV, receiving distance of 20cm, advancing speed of 0.5ml/H, diameter of a spinning needle head of 0.6mm, and spinning is carried out to form H 3 PW 12 O 40 @ ZIF-8/PAN electrospun nanofiber precursor;
(3) Finally, the obtained composite heteropolyacid@ZIF-8/PAN electrospun nanofiber precursor is carbonized at high temperature and subjected to in-situ phase transformation
Placing the composite heteropolyacid@ZIF-8/PAN electrospun nanofiber precursor obtained in the step (2) into a vacuum tube furnace, performing low-temperature pre-oxidation treatment in air, then heating at a heating rate of 10 ℃/min, and introducing an active atmosphere H when the temperature is raised to 800 ℃ under the protection of Ar gas 2 S, preserving heat for 2 hours to obtain the composite heteropoly acid/polymer electrostatic spinning nanofiber.
Example 11
(1) Firstly, preparing composite heteropolyacid@ZIF-8 composite nano particles
1.125g Zn (NO) 3 ) 2 6H 2 Zinc O nitrate was dissolved in 100mL of deionized water, to which was then added 1.113g of a heteropolyacid H 3 PW 12 O 40 And H is 3 PMo 12 O 40 Adding 13.75g of 2-methylimidazole into the solution after the mixture is uniformly dispersed according to the mass ratio of 2:1, stirring at room temperature for reaction for 24 hours, centrifuging and flushing with deionized water for three times to obtain composite heteropolyacid@ZIF-8 composite nano particles, and putting the composite nano particles into a vacuum drying oven for drying for later use;
(2) Then preparing the composite heteropolyacid@ZIF-8/PAN electrospun 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 simultaneously, and stirring to form a uniform solution; then, a high-voltage electrostatic spinning machine is used for setting electrostatic spinning parameter voltage of 20KV, receiving distance of 20cm, advancing speed of 0.5ml/H, diameter of a spinning needle head of 0.6mm, and spinning is carried out to form H 3 PW 12 O 40 @ ZIF-8/PAN electrospun nanofiber precursor;
(3) Finally, the obtained composite heteropolyacid@ZIF-8/PAN electrospun nanofiber precursor is carbonized at high temperature and subjected to in-situ phase transformation
Placing the composite heteropolyacid@ZIF-8/PAN electrospun nanofiber precursor obtained in the step (2) into a vacuum tube furnace, performing low-temperature pre-oxidation treatment in air, then heating at a heating rate of 10 ℃/min, and introducing an active atmosphere H when the temperature is raised to 800 ℃ under the protection of Ar gas 2 S, preserving heat for 2 hours to obtain the composite heteropoly acid/polymer electrostatic spinning nano-fiberDimension.
Example 12
(1) Firstly, preparing composite heteropolyacid@ZIF-8 composite nano particles
1.125g Zn (NO) 3 ) 2 6H 2 Zinc O nitrate was dissolved in 100mL of deionized water, to which was then added 1.113g of a heteropolyacid H 3 PW 12 O 40 And H is 3 PMo 12 O 40 Adding 13.75g of 2-methylimidazole into the solution after the mixture is uniformly dispersed according to the mass ratio of 1:2, stirring at room temperature for reaction for 24 hours, centrifuging and flushing with deionized water for three times to obtain composite heteropolyacid@ZIF-8 composite nano particles, and putting the composite nano particles into a vacuum drying oven for drying for later use;
(2) Then preparing the composite heteropolyacid@ZIF-8/PAN electrospun 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 simultaneously, and stirring to form a uniform solution; then, a high-voltage electrostatic spinning machine is used for setting electrostatic spinning parameter voltage of 20KV, receiving distance of 20cm, advancing speed of 0.5ml/H, diameter of a spinning needle head of 0.6mm, and spinning is carried out to form H 3 PW 12 O 40 @ ZIF-8/PAN electrospun nanofiber precursor;
(3) Finally, the obtained composite heteropolyacid@ZIF-8/PAN electrospun nanofiber precursor is carbonized at high temperature and subjected to in-situ phase transformation
Placing the composite heteropolyacid@ZIF-8/PAN electrospun nanofiber precursor obtained in the step (2) into a vacuum tube furnace, performing low-temperature pre-oxidation treatment in air, then heating at a heating rate of 10 ℃/min, and introducing an active atmosphere H when the temperature is raised to 800 ℃ under the protection of Ar gas 2 S, preserving heat for 2 hours to obtain the composite heteropoly acid/polymer electrostatic spinning nanofiber.
Example 13
(1) Firstly, preparing composite heteropolyacid@ZIF-67 composite nano particles
1.125g Co (NO) 3 ) 2 6H 2 Cobalt nitrate O was dissolved in 100mL of deionized water, to which was then added 1.113g of a heteropolyacid H 3 PW 12 O 40 And H is 3 PMo 12 O 40 After the mixture is uniformly dispersed, 13.75g of 2-methylimidazole is added into the solution, the mixture is stirred at room temperature for reaction for 24 hours, centrifuged and washed three times by deionized water to obtain H 3 PW 12 O 40 Putting the @ ZIF-67 composite nano particles into a vacuum drying oven for drying for later use;
(2) Then preparing a composite heteropolyacid@ZIF-67/PAN electrospun nanofiber precursor
Adding 0.5g of PAN and 0.5g of composite heteropolyacid @ ZIF-67 composite nano particles into 4.5g of DMF solution simultaneously, stirring to form a uniform solution, and setting an electrostatic spinning parameter voltage of 15KV by using a high-voltage electrostatic spinning machine; the receiving distance is 15cm; the propulsion rate is 0.5ml/h; the diameter of the spinning needle is 0.6mm, and H is formed by preparation 3 PW 12 O 40 @ ZIF-67/PAN electrospun nanofiber precursor;
(3) Finally, the obtained composite heteropolyacid@ZIF-67/PAN electrospun nanofiber precursor is carbonized at high temperature and subjected to in-situ phase transformation
Placing the composite heteropolyacid@ZIF-67/PAN electrospun nanofiber precursor obtained in the step (2) into a vacuum tube furnace, performing low-temperature pre-oxidation treatment in air, and then performing heating at a speed of 10 ℃/min; under the protection of Ar gas, when the temperature is raised to 800 ℃, the active atmosphere H is introduced 2 S, preserving heat for 2 hours to obtain the POM@MOFs/polymer electrostatic spinning nanofiber.
Example 14
(1) Firstly, preparing composite heteropolyacid@ZIF-67 composite nano particles
1.125g Co (NO) 3 ) 2 6H 2 Cobalt nitrate O was dissolved in 100mL of deionized water, to which was then added 1.113g of a heteropolyacid H 3 PW 12 O 40 And H is 3 PMo 12 O 40 After the mixture is uniformly dispersed, 13.75g of 2-methylimidazole is added into the solution according to the mass ratio of 2:1, the mixture is stirred at room temperature for reaction for 24 hours, and the mixture is centrifuged and washed three times by deionized water to obtain H 3 PW 12 O 40 Composite nano particle @ ZIF-67Drying the seeds in a vacuum drying oven for standby;
(2) Then preparing a composite heteropolyacid@ZIF-67/PAN electrospun nanofiber precursor
Adding 0.5g of PAN and 0.5g of composite heteropolyacid @ ZIF-67 composite nano particles into 4.5g of DMF solution simultaneously, stirring to form a uniform solution, and setting an electrostatic spinning parameter voltage of 15KV by using a high-voltage electrostatic spinning machine; the receiving distance is 15cm; the propulsion rate is 0.5ml/h; the diameter of the spinning needle is 0.6mm, and H is formed by preparation 3 PW 12 O 40 @ ZIF-67/PAN electrospun nanofiber precursor;
(3) Finally, the obtained composite heteropolyacid@ZIF-67/PAN electrospun nanofiber precursor is carbonized at high temperature and subjected to in-situ phase transformation
Placing the composite heteropolyacid@ZIF-67/PAN electrospun nanofiber precursor obtained in the step (2) into a vacuum tube furnace, performing low-temperature pre-oxidation treatment in air, and then performing heating at a speed of 10 ℃/min; under the protection of Ar gas, when the temperature is raised to 800 ℃, the active atmosphere H is introduced 2 S, preserving heat for 2 hours to obtain the POM@MOFs/polymer electrostatic spinning nanofiber.
Example 15
(1) Firstly, preparing composite heteropolyacid@ZIF-67 composite nano particles
1.125g Co (NO) 3 ) 2 6H 2 Cobalt nitrate O was dissolved in 100mL of deionized water, to which was then added 1.113g of a heteropolyacid H 3 PW 12 O 40 And H is 3 PMo 12 O 40 After the mixture is uniformly dispersed, 13.75g of 2-methylimidazole is added into the solution, the mixture is stirred at room temperature for reaction for 24 hours, and the mixture is centrifuged and washed three times by deionized water to obtain H 3 PW 12 O 40 Putting the @ ZIF-67 composite nano particles into a vacuum drying oven for drying for later use;
(2) Then preparing a composite heteropolyacid@ZIF-67/PAN electrospun nanofiber precursor
Adding 0.5g of PAN and 0.5g of composite heteropoly acid @ ZIF-67 composite nano particles into 4.5g of DMF solution simultaneously, stirring to form uniform solution, and then utilizingSetting an electrostatic spinning parameter voltage of 15KV by a high-voltage electrostatic spinning machine; the receiving distance is 15cm; the propulsion rate is 0.5ml/h; the diameter of the spinning needle is 0.6mm, and H is formed by preparation 3 PW 12 O 40 @ ZIF-67/PAN electrospun nanofiber precursor;
(3) Finally, the obtained composite heteropolyacid@ZIF-67/PAN electrospun nanofiber precursor is carbonized at high temperature and subjected to in-situ phase transformation
Placing the composite heteropolyacid@ZIF-67/PAN electrospun nanofiber precursor obtained in the step (2) into a vacuum tube furnace, performing low-temperature pre-oxidation treatment in air, and then performing heating at a speed of 10 ℃/min; under the protection of Ar gas, when the temperature is raised to 800 ℃, the active atmosphere H is introduced 2 S, preserving heat for 2 hours to obtain the POM@MOFs/polymer electrostatic spinning nanofiber.
Performance test:
the POM@MOFs/polymer electrospun nanofibers obtained in examples 1-15 were tested for their ORR/OER performance by the electrochemical workstation and rotating electrode device using a three electrode test method.
The sample preparation method of the working electrode comprises the following steps:
5mg of catalyst was weighed and dispersed in a mixed solution of ethanol/water (volume ratio 4:1) to prepare a catalyst solution, 6. Mu.L was applied dropwise to a rotating disk electrode having a diameter of 4mm, and the catalyst solution was dried naturally for use.
The three-electrode system uses a rotary disk electrode as a working electrode, an Ag/AgCl electrode as a reference electrode and a platinum wire electrode as a counter electrode.
Test conditions: introducing oxygen into 0.1M KOH solution for 30min to saturate ORR, and performing LSV curve test on ORR performance by using a linear sweep voltammogram; the LSV curve was used to test OER performance in a 1.0M KOH solution using a linear sweep voltammogram.
As shown in FIG. 1, the ORR electrocatalytic effect of POM@MOFs/polymer electrospun nanofibers obtained in example 1 shows by linear sweep voltammograms in the graph that the initial oxygen reduction potential of the catalyst obtained in example 1 is 0.93V and the limiting current density at 160 rpm is 5.21mA/cm -2 。
As shown in FIG. 2, the OER electrocatalytic effect of POM@MOFs/polymer electrospun nanofibers obtained in example 1 is shown by the linear sweep voltammogram in the graph to obtain a catalyst having a current density of 10mAcm obtained in example 1 -2 The corresponding oxygen evolution potential was 1.59V.
In the 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 160 rpm was 5.15mA/cm -2 。
In the OER electrocatalysis of POM@MOFs/Polymer electrospun nanofibers obtained in example 2, the catalyst current density obtained was 10mAcm -2 The corresponding oxygen evolution potential was 1.58V.
In the 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 160 rpm was 5.32mA/cm -2 。
In the OER electrocatalysis of POM@MOFs/Polymer electrospun nanofibers obtained in example 3, the catalyst current density obtained was 10mAcm -2 The corresponding oxygen evolution potential was 1.56V.
In the 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 160 rpm was 5.21mA/cm -2 。
In the OER electrocatalysis of POM@MOFs/Polymer electrospun nanofibers obtained in example 4, the catalyst current density obtained was 10mAcm -2 The corresponding oxygen evolution potential was 1.54V.
In the ORR electrocatalysis of POM@MOFs/Polymer electrospun nanofibers obtained in example 5, the initial oxygen reduction potential was 0.95V, and the limiting current density at 160 rpm was 5.22mA/cm -2 。
In OER electrocatalysis of POM@MOFs/Polymer electrospun nanofibers obtained in example 5, the catalyst current density obtained was 10mAcm -2 The corresponding oxygen evolution potential was 1.61V.
In the ORR electrocatalysis of POM@MOFs/polymer electrospun nanofibers obtained in example 6, the initial oxygen reduction potential was 0.90V,16Limiting current density at 00rpm was 5.03mA/cm -2 。
In the OER electrocatalysis of POM@MOFs/Polymer electrospun nanofibers obtained in example 6, the catalyst current density obtained was 10mAcm -2 The corresponding oxygen evolution potential was 1.65V.
In the 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 160 rpm was 5.17mA/cm -2 。
In OER electrocatalysis of POM@MOFs/Polymer electrospun nanofibers obtained in example 7, the catalyst current density obtained was 10mAcm -2 The corresponding oxygen evolution potential was 1.60V.
In the 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 160 rpm was 5.13mA/cm -2 。
In OER electrocatalysis of POM@MOFs/Polymer electrospun nanofibers obtained in example 8, the catalyst current density obtained was 10mAcm -2 The corresponding oxygen evolution potential was 1.63V.
In the 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 160 rpm was 5.26mA/cm -2 。
Example 9 OER electrocatalysis of POM@MOFs/Polymer electrospun nanofibers with a catalyst current density of 10mAcm -2 The corresponding oxygen evolution potential was 1.62V.
In the ORR electrocatalysis of POM@MOFs/polymer electrospun nanofibers obtained in example 10, the initial oxygen reduction potential was 0.96V and the limiting current density at 160 rpm was 5.36mA/cm -2 。
In OER electrocatalysis of POM@MOFs/Polymer electrospun nanofibers obtained in example 10, the catalyst current density obtained was 10mAcm -2 The corresponding oxygen evolution potential was 1.53V.
In the ORR electrocatalysis of POM@MOFs/polymer electrospun nanofibers obtained in example 11, the initial oxygen reduction potential wasThe limiting current density at 0.97V,160 rpm was 5.47mA/cm -2 。
In OER electrocatalysis of POM@MOFs/Polymer electrospun nanofibers obtained in example 11, the catalyst current density obtained was 10mAcm -2 The corresponding oxygen evolution potential was 1.50V.
In the 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 160 rpm was 5.56mA/cm -2 。
In OER electrocatalysis of POM@MOFs/Polymer electrospun nanofibers obtained in example 12, the catalyst current density obtained was 10mAcm -2 The corresponding oxygen evolution potential was 1.47V.
In the 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 160 rpm was 5.34mA/cm -2 。
In OER electrocatalysis of POM@MOFs/Polymer electrospun nanofibers obtained in example 13, the catalyst current density obtained was 10mAcm -2 The corresponding oxygen evolution potential was 1.54V.
In the 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 160 rpm was 5.63mA/cm -2 。
In OER electrocatalysis of POM@MOFs/Polymer electrospun nanofibers obtained in example 14, the catalyst current density obtained was 10mAcm -2 The corresponding oxygen evolution potential was 1.46V.
In the ORR electrocatalysis of POM@MOFs/polymer electrospun nanofibers obtained in example 15, the initial oxygen reduction potential was 0.97V and the limiting current density at 160 rpm was 5.52mA/cm -2 。
In OER electrocatalysis of POM@MOFs/Polymer electrospun nanofibers obtained in example 15, the catalyst current density obtained was 10mAcm -2 The corresponding oxygen evolution potential was 1.50V.
With the above-described preferred embodiments according to the present invention as an illustration, the above-described descriptions can be used by persons skilled in the relevant art to make various changes and modifications without departing from the scope of the technical idea of the present invention. The technical scope of the present invention is not limited to the description, but must be determined according to the scope of claims.

Claims (2)

1. The heteropolyacid@MOFs/polymer electrospun nanofiber is characterized by being prepared by the following steps:
(1) Preparing composite heteropolyacid@ZIF-8 composite nano particles
1.125g Zn (NO) 3 ) 2 6H 2 Zinc O nitrate was dissolved in 100mL deionized water, and 1.113g of a heteropolyacid H was added thereto 3 PW 12 O 40 And H is 3 PMo 12 O 40 Adding 13.75g of 2-methylimidazole into the solution after the mixture is uniformly dispersed according to the mass ratio of 1:2, stirring at room temperature for reaction 24h, centrifuging and flushing with deionized water for three times to obtain composite heteropolyacid@ZIF-8 composite nano particles, and putting the composite nano particles into a vacuum drying oven for drying for later use;
(2) Preparation of composite heteropolyacid @ ZIF-8/PAN electrospun nanofiber precursor
Adding 0.5g PAN and 0.5g composite heteropoly acid @ ZIF-8 composite nano particles into 4.5g DMF solution simultaneously, and stirring to form a uniform solution; then, a high-voltage electrostatic spinning machine is used for setting electrostatic spinning parameter voltage of 20KV, receiving distance of 20cm, advancing speed of 0.5ml/H, diameter of a spinning needle head of 0.6mm, and spinning is carried out to form H 3 PW 12 O 40 @ ZIF-8/PAN electrospun nanofiber precursor;
(3) High-temperature carbonization and in-situ phase transformation are carried out on the obtained composite heteropolyacid@ZIF-8/PAN electrospun nanofiber precursor
Placing the composite heteropolyacid@ZIF-8/PAN electrospun nanofiber precursor obtained in the step (2) into a vacuum tube furnace, performing low-temperature pre-oxidation treatment in air, then heating at a heating rate of 10 ℃/min, and introducing an active atmosphere H when the temperature is raised to 800 ℃ under the protection of Ar gas 2 S, preserving heat for 2 hours to obtain a complexThe hybrid heteropoly acid/polymer electrospun nanofibers.
2. The heteropolyacid@MOFs/polymer electrospun nanofiber is characterized by being prepared by the following steps:
(1) Preparing composite heteropolyacid@ZIF-67 composite nano particles
1.125g Co (NO) 3 ) 2 6H 2 Cobalt nitrate O was dissolved in 100mL deionized water, to which was then added 1.113g of a heteropolyacid H 3 PW 12 O 40 And H is 3 PMo 12 O 40 After the mixture is uniformly dispersed, 13.75g of 2-methylimidazole is added into the solution according to the mass ratio of 2:1, the mixture is stirred at room temperature for reaction for 24 hours, and the mixture is centrifuged and washed three times by deionized water to obtain H 3 PW 12 O 40 Putting the @ ZIF-67 composite nano particles into a vacuum drying oven for drying for later use;
(2) Preparation of composite heteropolyacid @ ZIF-67/PAN electrospun nanofiber precursor
Adding 0.5g of PAN and 0.5g of composite heteropolyacid @ ZIF-67 composite nano particles into 4.5g of DMF solution simultaneously, stirring to form a uniform solution, and setting an electrostatic spinning parameter voltage of 15KV by using a high-voltage electrostatic spinning machine; the receiving distance is 15cm; the propulsion rate is 0.5ml/h; the diameter of the spinning needle is 0.6mm, and H is formed by preparation 3 PW 12 O 40 @ ZIF-67/PAN electrospun nanofiber precursor;
(3) High-temperature carbonization and in-situ phase transformation are carried out on the obtained composite heteropolyacid@ZIF-67/PAN electrospun nanofiber precursor
Placing the composite heteropolyacid@ZIF-67/PAN electrospun nanofiber precursor obtained in the step (2) into a vacuum tube furnace, performing low-temperature pre-oxidation treatment in air, and then performing heating at a speed of 10 ℃/min; under the protection of Ar gas, when the temperature is raised to 800 ℃, the active atmosphere H is introduced 2 S, preserving heat for 2 hours to obtain the POM@MOFs/polymer electrostatic spinning nanofiber.
CN202111476549.4A 2021-12-06 2021-12-06 heteropolyacid@MOFs/polymer electrostatic spinning nanofiber Active CN114400339B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111476549.4A CN114400339B (en) 2021-12-06 2021-12-06 heteropolyacid@MOFs/polymer electrostatic spinning nanofiber

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111476549.4A CN114400339B (en) 2021-12-06 2021-12-06 heteropolyacid@MOFs/polymer electrostatic spinning nanofiber

Publications (2)

Publication Number Publication Date
CN114400339A CN114400339A (en) 2022-04-26
CN114400339B true CN114400339B (en) 2023-09-12

Family

ID=81225226

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111476549.4A Active CN114400339B (en) 2021-12-06 2021-12-06 heteropolyacid@MOFs/polymer electrostatic spinning nanofiber

Country Status (1)

Country Link
CN (1) CN114400339B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117954643A (en) * 2024-03-26 2024-04-30 淄博火炬能源有限责任公司 Heteropoly acid-based nitrogen-doped carbon catalyst material, preparation method thereof and method for preparing zinc-air battery by using same

Citations (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SI1923423T1 (en) * 2006-11-14 2013-11-29 Sociedad Anonima Minera Catalano-Aragonesa Process for the additivation of synthetic fibres, artificial fibres and polymers with special properties
US11969722B2 (en) * 2019-06-26 2024-04-30 Ffi Ionix Ip, Inc. Anionic membranes incorporating functional additives

Patent Citations (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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 (1)

* Cited by examiner, † Cited by third party
Title
顾翼东等.《化学词典》.上海辞书出版社,1989,第724页. *

Also Published As

Publication number Publication date
CN114400339A (en) 2022-04-26

Similar Documents

Publication Publication Date Title
CN113540478B (en) Porous carbon-based nanofiber film material loaded by metal single atom and metal derivative thereof, and preparation method and application thereof
CN111545241B (en) Cobalt phosphide-loaded heteroatom-doped porous carbon material, and preparation method and application thereof
CN106159287B (en) A kind of composite type fuel cell cathode catalyst NGPC/NCNTs and preparation method thereof
CN111682224B (en) Monoatomic cobalt-loaded nitrogen-doped graphite-like carbon cathode catalyst for metal-air battery
CN103441287B (en) The preparation method of a kind of direct methanol fuel cell membrane electrode
CN104549235B (en) A kind of preparation method of the immobilized nm Pt catalyst of carbon
CN109841854A (en) A kind of nitrogen-doped carbon-supported antozone reducing catalyst and preparation method thereof
CN113054207B (en) Preparation method of metal salt assisted rapid growth metal organic framework derivative
CN112354550B (en) Composite modified catalyst with through hole structure
CN108927185B (en) Oxygen reduction catalyst of heteroatom-doped carbon nanotube-loaded iron phosphide nanoparticles and preparation method thereof
CN103495432A (en) Method for preparing efficient stable fuel cell catalyst
CN106829924A (en) A kind of preparation method of one-dimensional porous CNT
CN114497585A (en) Preparation method of platinum-based synergistic catalyst with structure coupling effect
CN114784297B (en) Preparation method of monoatomic cobalt ORR catalyst
CN108579718B (en) Preparation method and application of indium-doped nano porous carbon material
CN114400339B (en) heteropolyacid@MOFs/polymer electrostatic spinning nanofiber
CN108198701B (en) Cobaltosic oxide/carbon composite electrode material, preparation method and application thereof
CN112701297A (en) High-stability non-noble metal catalyst electrode and preparation method and application thereof
CN113036160A (en) Preparation method of nanocellulose-derived carbon-supported cobalt electrocatalyst
CN114843536A (en) Iron-cobalt bimetallic oxygen reduction electro-catalytic material and preparation method and application thereof
CN104241664B (en) A kind of PtM/M '-PPy-C eelctro-catalyst for fuel cell oxygen reduction reaction and preparation method thereof
CN112357902A (en) Mesoporous carbon material with high specific surface area, and preparation method and application thereof
CN113948728B (en) Co-N doped directional pore carbon nanofiber electrocatalyst and preparation method and application thereof
CN113097510B (en) Preparation method of iron-based nitrogen-phosphorus co-doped porous carbon-oxygen reduction catalyst
CN115172770A (en) Gas diffusion electrode and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant