CN111939981A - CoFeMOF-P/b-CNF composite material electrocatalyst and preparation method thereof - Google Patents

CoFeMOF-P/b-CNF composite material electrocatalyst and preparation method thereof Download PDF

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CN111939981A
CN111939981A CN202010826311.9A CN202010826311A CN111939981A CN 111939981 A CN111939981 A CN 111939981A CN 202010826311 A CN202010826311 A CN 202010826311A CN 111939981 A CN111939981 A CN 111939981A
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CN111939981B (en
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许涵侨
祁璐
单学凌
钟雨声
王研
陈智栋
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Changzhou University
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Abstract

The invention belongs to the technical field of new materials, and particularly relates to a CoFeMOF-P/b-CNF composite material electrocatalyst and a preparation method thereof. The technical points are as follows: the CoFeMOF-P/b-CNF electrocatalyst comprises Co salt, Fe salt and bacterial cellulose membrane, and is subjected to high-temperature phosphorization by using phosphonium salt. According to the CoFeMOF-P/b-CNF composite material electrocatalyst and the preparation method thereof, the CNF prepared by taking the bacterial cellulose membrane as the precursor has the advantages of multiple three-dimensional structure pore channels and high toughness, and is used as a framework supporting material of CoFeMOF and a lead between MOFs particles, so that the complete morphology of the MOFs material is ensured, and the conductivity and the electrocatalytic capacity are improved.

Description

CoFeMOF-P/b-CNF composite material electrocatalyst and preparation method thereof
Technical Field
The invention belongs to the technical field of new materials, and particularly relates to a CoFeMOF-P/b-CNF composite material electrocatalyst and a preparation method thereof.
Background
Energy is the inexhaustible power for human development and is an important standard for measuring national economic development and quality of life of people. In the past decades, the rapid growth of population, the popularization of automobiles, and the increase in use of machines have resulted in the declining reserves of fossil fuels, and eventually the energy will be exhausted, and moreover, the use of fossil fuels has resulted in serious environmental pollution and global warming. Therefore, in recent years, people have been actively developing new environmentally friendly energy sources. The clean, pollution-free, sustainable resource, hydrogen energy, is recognized as the most promising alternative to fossil fuels in the 21 st century. The hydrogen production (HER) by electrocatalytic decomposition of water is a hydrogen production method which is simple and convenient to operate, can convert electric energy into chemical energy in an environment-friendly mode, can be combined with other intermittent energy sources (such as wind energy and solar energy) for use, and provides a solution for high-purity hydrogen production. However, the hydrogen evolution reaction, one of the essential reactions in the water splitting process, requires high electric power consumption. There is therefore a pressing need for effective HER catalysts to improve the efficiency of electrocatalytic hydrogen production. To date, platinum group metals are recognized as the most advanced and effective electrocatalysts, but their large-scale use in industry is limited due to their scarcity and high cost.
In view of the above-mentioned drawbacks of the prior art, the present inventors have conducted extensive practical experience and professional knowledge for many years in designing and manufacturing such products, and have conducted research and innovation in combination with the application of theory, in order to create a cofefmof-P/b-CNF composite material electrocatalyst and a preparation method thereof, which has good electrical conductivity, long-term electrochemical stability, good catalytic activity, low overpotential, large surface area and low cost. After continuous research and design and repeated trial production and improvement, the invention with practical value is finally created.
Disclosure of Invention
The invention aims to provide a CoFeMOF-P/b-CNF composite material electrocatalyst, a CNF prepared by taking a bacterial cellulose membrane as a precursor has the advantages of multiple three-dimensional structure pore canals and high toughness, and the CNF is used as a lead between a framework support material of CoFeMOF and MOFs particles, so that the morphology integrity of the MOFs material is ensured, the conductivity and the electrocatalytic capacity are improved, and the composite material electrocatalyst has good conductivity, long-term electrochemical stability, good catalytic activity, low overpotential, large surface area and low cost.
The technical purpose of the invention is realized by the following technical scheme:
the CoFeMOF-P/b-CNF composite material electrocatalyst provided by the invention comprises Co salt, Fe salt and a bacterial cellulose membrane, and is subjected to high-temperature phosphorization by virtue of phosphorus salt. The novel MOFs material and the derivatives thereof are used as a development catalyst, so that the reaction kinetics can be effectively promoted, the energy utilization rate is improved, and the catalytic performance of the electrochemical catalyst is improved.
Further, the Co salt is Co (NO)3)2、CoCl2Or Co (CH)3COO)2Any one of them, the concentration is 5-11 mg/mL.
Further, the Fe salt is Fe (NO)3)3、FeCl3Or Fe (CH)3COO)3Any one of the concentrations is 3-8 mg/mL.
Further, the Co salt and Fe salt are Co (CH) respectively3COO)2•6H2O and FeCl3•6H2O, concentration of each of Co (CH)3COO)2•6H2O 11mg/mL，FeCl3•6H2O 6mg/mL。
Further, the phosphorus salt is NaH2PO2Or KH2PO2The mass is 0.5 to 3 g.
The invention provides a preparation method of a CoFeMOF-P/b-CNF composite material electrocatalyst, which is used for preparing the CoFeMOF-P/b-CNF electrocatalyst through simple hydrothermal and phosphorization modes and has the same effect.
The technical effects of the invention are realized by the following technical scheme:
the invention provides a preparation method of a CoFeMOF-P/b-CNF composite material electrocatalyst, which comprises the following operation steps:
s1. preparation of cofefmof-loaded bacterial cellulose membranes: dissolving Co salt and Fe salt, adding into the bacterial cellulose membrane, shaking to enable the Co salt and the Fe salt to be uniformly adsorbed on the surface of the bacterial cellulose membrane, transferring the mixture to a high-pressure reaction kettle, and preparing the bacterial cellulose membrane loaded with CoFeMOF by a one-step hydrothermal method;
s2 preparation of CoFeMOF-P/b-CNF electrocatalyst: transferring the product obtained in the step S1 to a tubular furnace, putting phosphate into an upper air inlet of an air passage of the tubular furnace, introducing inert gas, carbonizing the bacterial cellulose membrane in the step S1 at high temperature, and simultaneously phosphorizing to obtain a CoFeMOF-P/b-CNF electrocatalyst; the electric catalyst after phosphorization can improve the conductivity of the electric catalyst due to the doping of the phosphorus element.
Preferably, in the step S1, the one-step hydrothermal method is to adsorb Co salt and Fe salt on the surface of the bacterial cellulose membrane in advance, and the adsorption time is 8-24 hours.
Preferably, the one-step hydrothermal method in step S1 is a hydrothermal reaction at 100-200 ℃ for 24-72 hours.
Preferably, the phosphating temperature in the step S2 is 200-400 ℃, and the phosphating time is 1-5 hours.
Preferably, in the above embodiment, the inert gas in step S2 is either nitrogen or argon.
In conclusion, the invention has the following beneficial effects:
(1) the Co salt and the Fe salt are dissolved and then mixed with the bacterial cellulose membrane in advance for adsorption, so that the adsorption capacity of the CoFeMOF prepared by a subsequent hydrothermal method on the surface of the bacterial cellulose is greatly increased, and the adsorption is more uniform;
(2) selecting (CNF) which has excellent performance, is environment-friendly, is simple to prepare and is industrially produced, and simultaneously obtaining carbon fibers in the high-temperature phosphating process, wherein the method is simple;
(3) the CNF prepared by taking the bacterial cellulose membrane as a precursor has the advantages of multiple three-dimensional structural pore canals and high toughness, is used as a lead between a framework supporting material of CoFeMOF and MOFs particles, ensures the complete appearance of the MOFs material, and improves the conductivity and the electrocatalytic capacity;
(4) CoFeMOF bimetal MOFs are selected to prepare the CoFeMOF-P/b-CNF electrocatalyst, and a new bimetal bond is introduced to promote the fracture of O-H and accelerate the formation of H-H bonds, so that the electrocatalytic performance of the catalyst is improved. And the bimetallic MOF has two metal centers and has more diversified catalytic active sites and adsorption sites compared with single metal MOF, so that the catalytic performance, the structural stability and the like are improved.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a scanning electron micrograph and schematic structural representation of a CoFeMOF-P/b-CNF electrocatalyst;
FIG. 2 is a plot of linear sweep voltammograms of CoFeMOF, CoFeMOF-P, CoFeMOF/b-CNF, CoFeMOF-P/b-CNF, and commercial Pt/C;
FIG. 3 is a graph of the Tafel slopes for CoFeMOF, CoFeMOF-P, CoFeMOF/b-CNF, CoFeMOF-P/b-CNF, and commercial Pt/C.
Detailed Description
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the present invention provides an electrocatalyst made of cofefmof-P/b-CNF composite material and its preparation method, and its specific embodiments, features and effects are described in detail below.
Example 1: CoFeMOF-P/b-CNF composite material electrocatalyst and preparation method thereof
The CoFeMOF-P/b-CNF composite material electrocatalyst comprises Co salt, Fe salt and a bacterial cellulose membrane, and is subjected to high-temperature phosphorization by virtue of phosphonium salt.
The preparation method comprises the following steps:
s1, preparing 10 mL of mixed solution of N, N-Dimethylformamide (DMF) and ethanol in a volume ratio of 1:1, and adding 11mg/mL of Co (CH)3COO)2•6H2O, 6 mg/mL FeCl3•6H2O, 6 mg/mL terephthalic acid and 50 mg/mL polyvinylpyrrolidone are dissolved uniformly at room temperature, then 1g of bacterial cellulose membrane is added, the mixture is shaken and adsorbed for 12 hours, and the mixture is transferred into a polytetrafluoroethylene reaction kettle and heated to 150 ℃ for hydrothermal reaction for 48 hours; after cooling to room temperature, washing with DMF for three times, and drying the brown-black product in an oven at 100 ℃ to obtain a bacterial cellulose membrane loaded with CoFeMOF;
s2, placing the bacterial cellulose membrane loaded with the CoFeMOF into a ceramic disc, placing the ceramic disc into a tube furnace, and simultaneously placing 1g of NaH at an upper air port of the tube furnace2PO2General formula N2Setting the phosphating temperature to 300 ℃, keeping the temperature for 2 hours, cooling to room temperature, washing and drying a product by using deionized water to obtain the CoFeMOF-P/b-CNF.
The scanning electron microscope image of the obtained product is shown in figure 1, the shuttle-shaped CoFeMOF is regular in shape, and the b-CNF is used as a framework supporting material of the CoFeMOF and a lead between CoFeMOF particles, so that the complete shape of the MOFs material is ensured. As shown in FIG. 2, the initial potential of the prepared CoFeMOF-P/b-CNF is 60 mV, and only 138 mV of overpotential (eta) is needed to reach 10mA/cm2The current density of (1). As shown in FIG. 3, the Tafel slope of the prepared CoFeMOF-P/b-CNF is 66.8 mV/dec, which is very close to 48.3 mV/dec of the commercial PtC catalyst, and compared with comparative examples 1, 2 and 3, the electrochemical performance of the prepared CoFeMOF-P/b-CNF electrocatalyst is greatly improved.
Comparative example 1
Comprises the following steps
S1, preparing 10 mL of mixed solution of N, N-Dimethylformamide (DMF) and ethanol in a volume ratio of 1:1, and adding 11mg/mL of Co (CH)3COO)2•6H2O, 6 mg/mL FeCl3•6H2O, 6 mg/mL terephthalic acid and 50 mg/mL polyvinylpyrrolidone, dissolved uniformly at room temperature, and then transferred to a Teflon reaction kettleHeating to 150 ℃ for hydrothermal reaction for 48h, cooling to room temperature, washing with DMF for three times, and drying the brownish black product in a drying oven at 100 ℃ to obtain CoFeMOF;
as shown in FIG. 2, the initial potential of the prepared CoFeMOF is 209mV, and the overpotential (eta) of 368mV can reach 10mA/cm2Compared with the current density of the embodiment 1, the current density of the catalyst is larger than the over potential of 138 mV of the embodiment 1, the same catalytic effect is achieved, and more electric energy needs to be consumed. And as shown in FIG. 3, the prepared CoFeMOF Tafel slope is 108.8 mV/dec, which is higher than 48.3 mV/dec of commercial Pt/C compared with example 1, and the catalytic effect is inferior to that of example 1. Therefore, the electrochemical performance of comparative example 1 was decreased compared to example 1 because the bacterial cellulose membrane was not added and the high temperature phosphating was not performed, compared to example 1.
Comparative example 2
The method comprises the following operation steps:
s1, preparing 10 mL of mixed solution of N, N-Dimethylformamide (DMF) and ethanol in a volume ratio of 1:1, and adding 11mg/mL of Co (CH)3COO)2•6H2O, 6 mg/mL FeCl3•6H2Dissolving O, 6 mg/mL terephthalic acid and 50 mg/mL polyvinylpyrrolidone uniformly at room temperature, transferring the mixture into a polytetrafluoroethylene reaction kettle, heating the mixture to 150 ℃, carrying out hydrothermal reaction for 48 hours, cooling the mixture to room temperature, washing the mixture with DMF for three times, and drying the brownish black product in a 100 ℃ oven to obtain CoFeMOF;
s2, placing the CoFeMOF in a porcelain plate, placing the porcelain plate in a tube furnace, and simultaneously placing 1g of NaH on an air inlet of the tube furnace2PO2General formula N2Setting the phosphating temperature to be 300 ℃, keeping the temperature for 2 hours, cooling to room temperature, washing and drying a product by using deionized water to obtain the CoFeMOF-P.
As shown in FIG. 2, the initial potential of the prepared CoFeMOF-P is 100mV, and the overpotential (eta) of 199mV is required to reach 10mA/cm2Compared with the current density of the embodiment 1, the current density of the catalyst is larger than the over potential of 138 mV of the embodiment 1, the same catalytic effect is achieved, and more electric energy needs to be consumed. And as shown in FIG. 3, the prepared CoFeMOF-P Tafel slopeIs 81.1 mV/dec, which is higher than 48.3 mV/dec of commercial Pt/C compared with example 1, and the catalytic effect is inferior to example 1. Therefore, it is understood from the results that the bacterial cellulose membrane was not added to comparative example 2, and the electrochemical performance of the electrocatalyst of example 1 was superior to that of comparative example 2.
Comparative example 3
The method comprises the following operation steps:
s1, preparing 10 mL of mixed solution of N, N-Dimethylformamide (DMF) and ethanol in a volume ratio of 1:1, and adding 11mg/mL of Co (CH)3COO)2•6H2O, 6 mg/mL FeCl3•6H2O, 6 mg/mL terephthalic acid and 50 mg/mL polyvinylpyrrolidone are dissolved uniformly at room temperature, 1g of bacterial cellulose membrane is added, the bacterial cellulose membrane is shaken and adsorbed for 12 hours, and the bacterial cellulose membrane is transferred to a polytetrafluoroethylene reaction kettle and heated to 150 ℃ for hydrothermal reaction for 48 hours. After cooling to room temperature, washing with DMF three times and drying the brown-black product in an oven at 100 ℃ to give cofefmof loaded bacterial cellulose membranes.
S2, placing the bacterial cellulose membrane loaded with the CoFeMOF into a ceramic disc, placing the ceramic disc into a tube furnace, and introducing N2The temperature was set at 300 ℃ for 2 hours. And after cooling to room temperature, washing and drying the product by using deionized water to obtain the CoFeMOF/b-CNF.
As shown in FIG. 2, the initial potential of the prepared CoFeMOF-P/b-CNF is 118mV, and the overpotential (eta) of 216mV can reach 10mA/cm2Compared with the current density of the embodiment 1, the current density of the catalyst is larger than the over potential of 138 mV of the embodiment 1, the same catalytic effect is achieved, and more electric energy needs to be consumed. And as shown in FIG. 3, the prepared CoFeMOF/b-CNF Tafel slope is 66.8 mV/dec, which is higher than 48.3 mV/dec of commercial Pt/C compared with example 1, and the catalytic effect is inferior to that of example 1. Comparative example 3 was not subjected to high temperature phosphating, which resulted in a decrease in the electrochemical performance of the electrocatalyst of comparative example 3, as compared to example 1.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (10)

1. The CoFeMOF-P/b-CNF composite material electrocatalyst is characterized in that the CoFeMOF-P/b-CNF electrocatalyst comprises a Co salt, a Fe salt and a bacterial cellulose membrane, and the CoFeMOF-P/b-CNF electrocatalyst is subjected to high-temperature phosphorization through a phosphonium salt.
2. The cofmof-P/b-CNF composite electrocatalyst according to claim 1, wherein said Co salt is Co (NO)3)2、CoCl2Or Co (CH)3COO)2Any one of them, the concentration is 5-11 mg/mL.
3. The cofmof-P/b-CNF composite electrocatalyst according to claim 1 or 2, characterized in that said Fe salt is Fe (NO)3)3、FeCl3Or Fe (CH)3COO)3Any one of the concentrations is 3-8 mg/mL.
4. The cofmof-P/b-CNF composite electrocatalyst according to claim 1, wherein the Co salt and Fe salt are Co (CH) respectively3COO)2•6H2O and FeCl3•6H2O, concentration of each of Co (CH)3COO)2•6H2O 11mg/mL，FeCl3•6H2O 6mg/mL。
5. The cofmof-P/b-CNF composite electrocatalyst according to claim 1, wherein the phosphorus salt is NaH2PO2Or KH2PO2Of mass is0.5~3g。
6. A preparation method of a CoFeMOF-P/b-CNF composite material electrocatalyst is characterized by comprising the following operation steps:
s1. preparation of cofefmof-loaded bacterial cellulose membranes: dissolving Co salt and Fe salt with deionized water, adding the Co salt and the Fe salt into a bacterial cellulose membrane, shaking to enable the Co salt and the Fe salt to be uniformly adsorbed on the surface of the bacterial cellulose membrane, transferring the mixture to a high-pressure reaction kettle, and preparing the bacterial cellulose membrane loaded with CoFeMOF by a one-step hydrothermal method;
s2 preparation of CoFeMOF-P/b-CNF electrocatalyst: and (4) transferring the product obtained in the step S1 to a tubular furnace, putting phosphate into an upper air inlet of an air passage of the tubular furnace, introducing inert gas, carbonizing the bacterial cellulose membrane obtained in the step S1 at high temperature, and simultaneously phosphorizing to obtain the CoFeMOF-P/b-CNF electrocatalyst.
7. The preparation method of the CoFeMOF-P/b-CNF composite material electrocatalyst according to claim 6, wherein the one-step hydrothermal method in the step S1 is to adsorb Co salt and Fe salt on the surface of a bacterial cellulose membrane in advance, and the adsorption time is 8-24 hours.
8. The preparation method of the CoFeMOF-P/b-CNF composite material electrocatalyst according to claim 6 or 7, wherein the one-step hydrothermal method in the step S1 is a hydrothermal reaction at 100-200 ℃ for 24-72 hours.
9. The preparation method of the CoFeMOF-P/b-CNF composite material electrocatalyst according to claim 8, wherein the phosphating temperature in the step S2 is 200-400 ℃, and the phosphating time is 1-5 hours.
10. The method for preparing the CoFeMOF-P/b-CNF composite material electrocatalyst according to claim 8, wherein the inert gas of the step S2 is any one of nitrogen or argon.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112481638A (en) * 2020-11-27 2021-03-12 常州大学 Bio-based carbon material loaded inorganic compound electrocatalyst and preparation method thereof
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CN113699556A (en) * 2021-08-27 2021-11-26 常州大学 CoNiMOF-BP QDs/b-CNF composite material electrocatalyst and preparation method thereof
CN114520341A (en) * 2022-01-12 2022-05-20 河北大学 Electro-catalytic composite material based on bacterial cellulose and preparation method and application thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108550821A (en) * 2018-04-25 2018-09-18 华东师范大学 A kind of preparation method of nucleocapsid nickel phosphide/carbosphere based on Ni-MOF
CN109166733A (en) * 2018-09-30 2019-01-08 北京印刷学院 A kind of method that hydro-thermal method prepares Ni/Co base MOF material
CN109926084A (en) * 2019-04-04 2019-06-25 西安交通大学 One kind is based on hydrogen reduction/analysis oxygen double-function catalyzing material and preparation method derived from more metal MOFs
CN109926083A (en) * 2019-03-25 2019-06-25 湖北大学 A kind of bimetallic Fe-Co nitride elctro-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
CN110354876A (en) * 2019-07-19 2019-10-22 南京理工大学 A kind of hollow Ni2P/Co2P/Fe2The preparation method of the nano combined elctro-catalyst of P

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108550821A (en) * 2018-04-25 2018-09-18 华东师范大学 A kind of preparation method of nucleocapsid nickel phosphide/carbosphere based on Ni-MOF
CN109166733A (en) * 2018-09-30 2019-01-08 北京印刷学院 A kind of method that hydro-thermal method prepares Ni/Co base MOF material
CN109926083A (en) * 2019-03-25 2019-06-25 湖北大学 A kind of bimetallic Fe-Co nitride elctro-catalyst and the preparation method and application thereof
CN109926084A (en) * 2019-04-04 2019-06-25 西安交通大学 One kind is based on hydrogen reduction/analysis oxygen double-function catalyzing material and preparation method derived from more metal MOFs
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
CN110354876A (en) * 2019-07-19 2019-10-22 南京理工大学 A kind of hollow Ni2P/Co2P/Fe2The preparation method of the nano combined elctro-catalyst of P

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112481638A (en) * 2020-11-27 2021-03-12 常州大学 Bio-based carbon material loaded inorganic compound electrocatalyst and preparation method thereof
CN113075269A (en) * 2021-03-26 2021-07-06 常州大学 Electrochemical luminescence aptamer sensor for specifically detecting chloramphenicol and preparation method and application thereof
CN113075269B (en) * 2021-03-26 2023-01-17 常州大学 Electrochemical luminescence aptamer sensor for specifically detecting chloramphenicol and preparation method and application thereof
CN113699556A (en) * 2021-08-27 2021-11-26 常州大学 CoNiMOF-BP QDs/b-CNF composite material electrocatalyst and preparation method thereof
CN114520341A (en) * 2022-01-12 2022-05-20 河北大学 Electro-catalytic composite material based on bacterial cellulose and preparation method and application thereof

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