CN113299492A - MOF-derived porous metal phosphide nanosheet array and application thereof - Google Patents

MOF-derived porous metal phosphide nanosheet array and application thereof Download PDF

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CN113299492A
CN113299492A CN202110634176.2A CN202110634176A CN113299492A CN 113299492 A CN113299492 A CN 113299492A CN 202110634176 A CN202110634176 A CN 202110634176A CN 113299492 A CN113299492 A CN 113299492A
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copper
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CN113299492B (en
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金玉红
李乐园
张倩倩
刘晶冰
汪浩
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Beijing University of Technology
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Abstract

An MOF derived porous metal phosphide nanosheet array and application thereof, belonging to the technical field of MOF derivative supercapacitor materials. Using nickel chloride hexahydrate (NiCl)2·6H2O), terephthalic acid (PTA) and foam copper are subjected to reduction phosphorization under relatively mild conditions to prepare an electrode material-foam base with excellent supercapacitor performanceIn-situ growth of carbon-coated Ni on substrate2Porous nanoarrays of P (Ni)2P/C @ substrate). The material has good redox reversible performance.

Description

MOF-derived porous metal phosphide nanosheet array and application thereof
Technical Field
The invention relates to carbon-coated Ni based on in-situ growth on foam copper2P/Cu3P porous nanoarrays (Ni)2P/C@Cu3P-CF), belonging to the technical field of MOF derivative super capacitor materials.
Background
The economy of China is rapidly increased, and various industries of China gradually make outstanding contributions to the economic development. Under such a large background, China does not forget to be a responsible image of the large country, and continuously makes self contribution to the problems of global energy exhaustion, environmental protection and the like: the research and development of new energy sources are greatly promoted, the development of the technical research of the new energy sources is fully promoted, and the Chinese scheme is continuously provided for solving the energy problems of the country and all countries in the world.
In the field of energy storage, there are advantages and disadvantages in the selection of batteries and capacitors: the battery has the advantages of high energy density, strong persistence and the like, but also has the defects of long charging time and large energy loss; the capacitor has the problems of extremely high charge and discharge rate and strong instantaneous power intensity, but the capacitor is low in capacity and low in durability. To solve these problems, batteries are often used in combination with capacitors, with complementary advantages. Under the background, the appearance of the super capacitor with pseudo-capacitance performance provides a new solution for the problem, the pseudo-capacitance performance has the advantages of high charging rate of the capacitor and high power density of the battery, and a new idea is provided for solving the future energy storage problem of China and even the world.
In the field of pseudocapacitive supercapacitors, the requirements for such supercapacitors are that they should be compatible: the power density is large, the rate capability is good, the cycling stability is excellent, and meanwhile, in order to meet the application requirements under different conditions in the technical field, the material cost is required to be relatively low, and the corresponding technical method can have certain structural functions on different substrates, namely, the preparation method has the characteristic of universality.
The invention researches a method for growing a porous nanosheet array on the foam copper by using nickel phosphide and copper phosphide, and the application of the material in the super capacitor has the characteristics of high energy density, good rate capability, good stability and low cost. Meanwhile, the method has good universality, can grow on different substrates, and can meet the production requirements under different conditions.
Disclosure of Invention
Aiming at the research foundation of the current MOFs super capacitor, the invention provides a method for utilizing nickel chloride hexahydrate (NiCl)2·6H2O), terephthalic acid (PTA) and foam copper are subjected to reduction phosphorization under relatively mild conditions to prepare the electrode material with excellent supercapacitor performance, namely the in-situ grown carbon-coated Ni on the foam substrate2Porous nanoarrays of P (Ni)2P/C @ substrate). The material has good redox reversible performance, and the technical scheme of the invention is realized by adopting the following mode.
Ni based on carbon coating2P/Cu3The preparation method of the supercapacitor electrode material with P growing on the foam copper in situ is characterized by comprising the following steps:
(1) foam copper pretreatment: cutting the foam copper into proper size (1 × 3 cm)2) Cleaning the surface with deoiling liquid, which is acetone solution, ultrasonically cleaning the foamy copper in an ultrasonic cleaning machine at room temperature for 30min, and washing away surface lipid; in order to remove the copper oxide on the surface layer of the copper foam, active sites need to be added, and then the copper foam is transferred into an acid solution (2M HCl) for ultrasonic cleaning for 15min, and then the copper foam is cleaned with a large amount of deionized water for several times and dried in a vacuum drying oven for standby.
(2) In-situ growth of Ni-MOF @ CF precursors: 2mmol of NiCl2·6H2O and 2mmol of terephthalic acid (PTA) are added into a conical flask, 40ml of N, N-Dimethylformamide (DMF) is added into magnetons, and the mixture is stirred for 30min on a magnetic stirrer; slowly adding 2ml deionized water dropwise while stirring with burette, transferring to 1 × 3cm after the above treatment2And (3) adding the foamy copper in the vacuum drying oven into a 100ml hydrothermal kettle, then adding the foamy copper into the hydrothermal kettle, transferring the hydrothermal kettle into an electric air drying oven after soaking, gradually heating to 120 ℃, keeping the temperature for 180min, naturally cooling to room temperature, taking out the prepared material, slowly cleaning with DMF, then adding into methanol, ultrasonically cleaning for 30s, taking out the material, and storing in a vacuum 80 ℃ drying oven for later use. And preparing light green uniform flaky Ni-MOF @ CF.
(3) Reduction phosphating
And putting the Ni-MOF @ CF into a tubular furnace, setting a temperature rise program of 5 ℃/min to be heated to 400 ℃, keeping the temperature for 120min in a hydrogen argon atmosphere, naturally cooling to room temperature, and taking out a sample. Subjecting the sample to CVD (chemical vapor deposition) to remove NaH2PO3150mg is placed at the upstream of a porcelain ark, the porcelain ark is placed in a tube furnace and is heated and insulated under the condition that nitrogen is used as protective gas and the gas flow rate is 50ml/min, the heating procedure is 2 ℃/min to 300 ℃, the insulation is carried out for 60min, the porcelain ark is naturally cooled to the room temperature and then taken out, and then Ni is obtained2P/C@Cu3The P-CF preparation is complete.
The foam copper can be replaced by foam nickel and carbon cloth, and finally the MOF derived porous single metal nickel phosphide nanosheet array is obtained, namely the final product is Ni2P/C @ foamed nickel, Ni2P/C @ carbon cloth.
The MOF-derived porous metal phosphide nanosheet array structure Ni2P/C@Cu3P-CF、Ni2P/C @ foamed nickel, Ni2The application of the P/C @ carbon cloth as an electrode material of a super capacitor.
The material obtained by the invention has excellent redox reversible performance and hydrophilicity, especially Ni2P/C@Cu3The P-CF also has the advantages of large capacity, good rate capability and good cycle stability as a capacitive material.
Drawings
FIG. 1 Ni-loaded material prepared in example 1 of the present invention2P/C@Cu3XRD pattern of P-CF nanoarrays.
FIG. 2 Ni prepared according to example 1 of the present invention2P/C@Cu3SEM images of P-CF nanoarrays at different magnifications.
FIG. 3 Ni prepared according to example 1 of the present invention2P/C@Cu3CV plots for P-CF nanoarrays at different sweep rates.
FIG. 4 Ni prepared according to example 1 of the present invention2P/C@Cu3GCD plots of P-CF nanoarrays at different sweep rates.
FIG. 5 Ni prepared according to example 1 of the present invention2P/C@Cu320mAcm of P-CF nano array2Capacity fade graph at rate of charge and discharge.
FIG. 6 Ni prepared according to example 2 of the present invention2P/C@Cu3Contact angle test pattern of P-CF nano array.
FIG. 7 is a magnified experimental image of a Ni-MOF @ CF nanoarray prepared in example 3 of the present invention.
FIG. 8 is an SEM micrograph of Ni-MOF @ NiF nanosheet arrays and Ni-MOF @ CC nanosheet arrays prepared in example 4 of the present invention.
Detailed Description
The essential features and the significant advantages of the invention will be further elucidated below, without being limited thereto, with reference to the accompanying drawings and the specific embodiments.
Example 1
(1) Cutting the foam copper into proper size (1 × 3 cm)2) Cleaning the surface with deoiling liquid, which is acetone solution, ultrasonic cleaning in ultrasonic cleaning machine at room temperature for 30min, and washing off surface lipid. In order to wash away impurities such as copper foam surface oxide after deoiling, it is necessary to transfer it into an acid solution (2)MHCl), simultaneously adding active sites of the foamy copper, then ultrasonically cleaning for 15min at room temperature to remove copper oxide on the surface layer, taking out, cleaning with a large amount of deionized water for several times, and drying in a vacuum drying oven for later use.
(2) 2mmol of NiCl2·6H2O and 2mmol of terephthalic acid (PTA) were added to a flask, 40ml of N, N-Dimethylformamide (DMF) was added to the flask and stirred on a magnetic stirrer for 30 min. Slowly dropwise adding 2ml deionized water into a burette while stirring, transferring the deionized water into a 100ml hydrothermal kettle, then adding the foamy copper into the vacuum drying oven into the hydrothermal kettle, and transferring the hydrothermal kettle into an electric air blowing drying oven after soaking. And (3) gradually heating the sample to 120 ℃ in an electric air drying box, preserving the temperature for 180min, naturally cooling to room temperature, taking out the prepared material, slowly cleaning with DMF, adding into methanol, performing ultrasonic treatment for 30s, taking out the material to obtain the light green uniform flaky Ni-MOF @ CF, and storing the Ni-MOF @ CF in a vacuum drying box at 80 ℃ for later use.
(3) Putting the Ni-MOF @ CF into a tube furnace in a hydrogen argon atmosphere, setting the temperature to be increased to 400 ℃ at a rate of 5 ℃/min and keeping the temperatureHeating for 120min, naturally cooling to room temperature, taking out the sample, and treating NaH by CVD (chemical vapor deposition)2PO3150mg was placed upstream of the porcelain ark in a tube furnace. Heating at nitrogen flow rate of 50ml/min, setting the temperature at 2 deg.C/min to 300 deg.C, and maintaining for 60 min. Naturally cooling to room temperature, and taking out the sample, namely Ni2P/C@Cu3The P-CF preparation is complete.
(4) To Ni2P/C@Cu3XRD measurement of P-CF nanosheet array referring specifically to FIG. 1, the above-mentioned Ni is2P/C@Cu3P-CF nano sheet array used as working electrode in three-electrode system (counter electrode: graphite electrode, reference electrode: mercury oxide electrode) (1)MPotassium hydroxide)). In a voltage range of 0-0.6V, the material has the advantages of large capacity, good multiplying power performance and good cyclic stability through cyclic sweep voltammetry (CV) at different sweep speeds, constant current charge-discharge curve (GCD) curves at different current densities and 5000 times of constant current charge-discharge curves, and particularly as shown in fig. 2, fig. 3, fig. 4 and fig. 5. Thus, Ni having excellent electrochemical properties was obtained2P/C@Cu3An array of P-CF nanosheets.
Example 2
(1) Cutting the foam copper into proper size (1 × 3 cm)2) Cleaning the surface with deoiling liquid, which is acetone solution, ultrasonic cleaning in ultrasonic cleaning machine at room temperature for 30min, and washing off surface lipid. In order to wash away impurities such as copper foam surface oxide after deoiling, it is necessary to transfer it into an acid solution (2)MHCl), simultaneously adding active sites of the foamy copper, then ultrasonically cleaning for 15min at room temperature to remove copper oxide on the surface layer, taking out, cleaning with a large amount of deionized water for several times, and drying in a vacuum drying oven for later use.
(2) 2mmol of NiCl2·6H2O and 2mmol of terephthalic acid (PTA) were added to a flask, 40ml of N, N-Dimethylformamide (DMF) was added to the flask and stirred on a magnetic stirrer for 30 min. Slowly dropwise adding 2ml deionized water into a burette while stirring, transferring the deionized water into a 100ml hydrothermal kettle, then adding the foamy copper into the vacuum drying oven into the hydrothermal kettle, and transferring the hydrothermal kettle into an electric air blowing drying oven after soaking. In the electricityAnd gradually heating the sample to 120 ℃ in a forced air drying oven, preserving the temperature for 180min, naturally cooling to room temperature, taking out the prepared material, slowly cleaning with DMF, adding into methanol, ultrasonically cleaning for 30s, taking out the material to obtain the light green uniform sheet-shaped Ni-MOF @ CF, and storing the Ni-MOF @ CF in a vacuum drying oven at 80 ℃ for later use.
(3) Putting the Ni-MOF @ CF into a tube furnace, heating to 400 ℃ at a temperature of 5 ℃/min, keeping the temperature for 120min, naturally cooling to room temperature, taking out a sample, and using a Chemical Vapor Deposition (CVD) method to carry out NaH2PO3150mg was placed upstream of the porcelain ark in a tube furnace. Heating at nitrogen flow rate of 50ml/min, setting the temperature at 2 deg.C/min to 300 deg.C, and maintaining for 60 min. Naturally cooling to room temperature, and taking out the sample, namely Ni2P/C@Cu3The P-CF preparation is complete.
(4) Mixing Ni2P/C@Cu3The P-CF nanosheets are placed on a glass slide of a contact angle measuring instrument, deionized water is sucked by a superfine needle tube, and the process that liquid drops drop and disappear is continuously recorded by a continuous recording camera at the moment when the liquid drops drop. After shooting, the liquid drops are contacted with the sheet, and a picture of the absorption process is taken out, so that the ultrathin nanosheet is found to have extremely strong water absorption property, and the liquid drops are absorbed within three thousandth of a second. While the contact angle is shown in figure 6.
Example 3
(1) Cutting the foam copper into 4 times (4 × 3 cm)2) Cleaning the surface with deoiling liquid, which is acetone solution, ultrasonic cleaning in ultrasonic cleaning machine at room temperature for 30min, and washing off surface lipid. In order to wash away impurities such as copper foam surface oxide after deoiling, it is necessary to transfer it into an acid solution (2)MHCl), simultaneously adding active sites of the foamy copper, then ultrasonically cleaning for 15min at room temperature to remove copper oxide on the surface layer, taking out, cleaning with a large amount of deionized water for several times, and drying in a vacuum drying oven for later use.
(2) 2mmol of NiCl2·6H2O and 2mmol of terephthalic acid (PTA) were added to a flask, 40ml of N, N-Dimethylformamide (DMF) was added to the flask and stirred on a magnetic stirrer for 30 min. Slowly dropping 2ml deionized water with stirring using a burette, transferring the water to a 100ml hydrothermal kettle, and then addingAnd adding the foam copper in the vacuum drying box into the hydrothermal kettle, and transferring the hydrothermal kettle into an electric drum air drying box after soaking. And (3) gradually heating the sample to 120 ℃ in an electric air drying box, preserving the temperature for 180min, naturally cooling to room temperature, taking out the prepared material, slowly cleaning with DMF, adding into methanol, ultrasonically cleaning for 30s, taking out the material to obtain the uniform light green flaky Ni-MOF @ CF, and storing the uniform light green flaky Ni-MOF @ CF in a vacuum drying box at 80 ℃ for later use.
(3) The appearance of a nanosheet array of Ni-MOF @ CF is observed, and the growth condition and the 1-fold size (1 x 3 cm) of the nanosheet array are found2) The flaky growth conditions are the same, and the presented light green color is basically consistent, so that the amplified experiment can be performed. As shown in fig. 7.
Example 4
(1) Cutting foamed nickel into proper size (1 × 3 cm)2) Cleaning the surface with deoiling liquid, which is acetone solution, ultrasonic cleaning in ultrasonic cleaning machine at room temperature for 30min, and washing off surface lipid. In order to wash off impurities such as deoiled foam nickel surface oxide, the impurities need to be transferred into an acid solution (2M HCl), active sites of the foam nickel are added at the same time, ultrasonic cleaning is carried out at room temperature for 15min to remove nickel oxide on the surface layer, and after the impurities are taken out, a large amount of deionized water is used for cleaning for several times and drying is carried out in a vacuum drying oven for standby.
(2) Cutting the carbon cloth into appropriate size (1 × 3 cm)2) Cleaning the surface with deoiling liquid, which is acetone solution, ultrasonic cleaning in ultrasonic cleaning machine at room temperature for 30min, and washing off surface lipid. In order to wash off impurities such as deoiled foamy copper surface oxides, the impurities need to be transferred into an acid solution (2M HCl), active sites of foamy copper are added at the same time, ultrasonic cleaning is carried out at room temperature for 15min to remove copper oxide on the surface layer, and after the impurities are taken out, a large amount of deionized water is used for cleaning for several times and drying is carried out in a vacuum drying oven for later use.
(3) 2mmol of NiCl2·6H2O and 2mmol of terephthalic acid (PTA) were added to a flask, 40ml of N, N-Dimethylformamide (DMF) was added to the flask and stirred on a magnetic stirrer for 30 min. Slowly dropwise adding 2ml deionized water under stirring using a burette, transferring the water into a 100ml hydrothermal kettle, and then drying the above vacuum drying ovenThe foamed nickel in the water is also added into the hydrothermal kettle for soaking. After soaking, the hydrothermal kettle is transferred to an electric air blowing drying box. And (3) gradually heating the sample to 120 ℃ in an electric air drying box, preserving the temperature for 180min, naturally cooling to room temperature, taking out the prepared material, slowly cleaning with DMF, adding into methanol, ultrasonically cleaning for 30s, taking out the material to obtain light green flaky Ni-MOF @ NiF, and storing the Ni-MOF @ NiF in a vacuum drying box at 80 ℃ for later use.
(4) 2mmol of NiCl2·6H2O and 2mmol of terephthalic acid (PTA) were added to a flask, 40ml of N, N-Dimethylformamide (DMF) was added to the flask and stirred on a magnetic stirrer for 30 min. Slowly dripping 2ml deionized water into the hydrothermal kettle of 100ml by using a burette while stirring, and then adding the carbon cloth in the vacuum drying oven into the hydrothermal kettle for soaking. After soaking, the hydrothermal kettle is transferred to an electric air blowing drying box. And (3) gradually heating the sample to 120 ℃ in an electric air drying box, preserving the temperature for 180min, naturally cooling to room temperature, taking out the prepared material, slowly cleaning with DMF, adding into methanol, ultrasonically cleaning for 30s, taking out the material which is light green sheet-shaped Ni-MOF @ CC, and storing in a vacuum drying box at 80 ℃ for later use.
(5) The SEM images of the Ni-MOF @ NiF nanosheet array and the Ni-MOF @ CC nanosheet array are determined, and particularly, as shown in FIG. 8, the growth condition is good, and the method can be used for growth of other types of substrates, namely has universality. And then further carbonizing and phosphorizing.

Claims (4)

1. Ni based on carbon coating2P/Cu3The preparation method of the supercapacitor electrode material with P growing on the foam copper in situ is characterized by comprising the following steps:
(1) foam copper pretreatment: cutting the foamy copper into a proper size, cleaning the surface by using degreasing liquid, wherein the degreasing liquid is an acetone solution, ultrasonically cleaning the foamy copper in an ultrasonic cleaning machine for 30min at room temperature, and washing away surface lipid; in order to remove copper oxide on the surface layer of the foam copper and increase the number of active sites, the foam copper is transferred into an acid solution for ultrasonic cleaning for 15min, and then is cleaned with ionized water for several times and dried in a vacuum drying oven for standby;
(2) in-situ growth of Ni-MOF @ CF precursors: 2mmol of NiCl2·6H2O and 2mmol of terephthalic acid (PTA) are added into a conical flask, 40ml of N, N-Dimethylformamide (DMF) is added into magnetons, and the mixture is stirred for 30min on a magnetic stirrer; slowly adding 2ml deionized water dropwise while stirring with burette, transferring to 1 × 3cm after the above treatment2And (3) adding the foamy copper in the vacuum drying oven into a 100ml hydrothermal kettle, then adding the foamy copper into the hydrothermal kettle, transferring the hydrothermal kettle into an electric air drying oven after soaking, gradually heating to 120 ℃, keeping the temperature for 180min, naturally cooling to room temperature, taking out the prepared material, slowly cleaning with DMF, then adding into methanol, ultrasonically cleaning for 30s, taking out the material, and storing in a vacuum 80 ℃ drying oven for later use. (ii) a Preparing light green uniform flaky Ni-MOF @ CF;
(3) reduction phosphating
And putting the Ni-MOF @ CF into a tubular furnace, setting a temperature rise program of 5 ℃/min to be heated to 400 ℃, keeping the temperature for 120min in a hydrogen argon atmosphere, naturally cooling to room temperature, and taking out a sample. Subjecting the sample to CVD treatment with NaH2PO3150mg is placed at the upstream of a porcelain ark, the porcelain ark is placed in a tube furnace and is heated and insulated under the condition that nitrogen is used as protective gas and the gas flow rate is 50ml/min, the heating procedure is 2 ℃/min to 300 ℃, the insulation is carried out for 60min, the porcelain ark is naturally cooled to the room temperature and then taken out, and then Ni is obtained2P/C@Cu3The P-CF preparation is complete.
2. A preparation method of an MOF-derived porous metal phosphide nanosheet array structure material is characterized in that the foamed copper in claim 1 is replaced by foamed nickel and carbon cloth, and an MOF-derived porous single-metal nickel phosphide nanosheet array is finally obtained, namely the final product is Ni2P/C @ foamed nickel, Ni2P/C @ carbon cloth.
3. MOF-derived porous metal phosphide nanosheet array structure Ni2P/C@Cu3P-CF、Ni2P/C @ foamed nickel, Ni2P/C @ carbon cloth, said Ni2P/C@Cu3P-CF、Ni2P/C @ foamed nickel, Ni2The P/C @ carbon cloth is prepared according to the process of claim 1 or 2.
4. MOF-derived porous metal phosphide nanosheet array structure Ni2P/C@Cu3P-CF、Ni2P/C @ foamed nickel, Ni2Application of P/C @ carbon cloth as super capacitor electrode material, and Ni2P/C@Cu3P-CF、Ni2P/C @ foamed nickel, Ni2The P/C @ carbon cloth is prepared according to the process of claim 1 or 2.
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CN113948727A (en) * 2021-09-30 2022-01-18 华南理工大学 MOF-based derived non-noble metal phosphide/carbon composite hydrazine oxidation catalyst and preparation method and application thereof

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